Chapter 7

ALE. The fermented infusion of pale malted barley, usually combined with infusion of hops. SeeBeer.

ALEMBIC, aStill; which see.

ALEMBROTH, salt of. The salt of wisdom, of the alchemists; a compound of bichloride of mercury and sal ammoniac, from which the old white precipitate of mercury is made.

ALGAROTH, powder of. A compound of oxide and chloride of antimony, being a precipitate obtained by pouring water into the acidulous chloride of that metal.

ALIZARINE. SeeMadder.

ALKALI. A class of chemical bodies, distinguished chiefly by their solubility in water, and their power of neutralising acids, so as to form saline compounds. The alkalis of manufacturing importance are, ammonia, potash, soda, and quinia. These alkalis change the purple colour of red cabbage and radishes to a green, the reddened tincture of litmus to a purple, and the colour of turmeric and many other yellow dyes to a brown. Even when combined with carbonic acid, the first three alkalis exercise this discolouring power, which the alkaline earths, lime and barytes, do not. The same three alkalis have an acrid, and somewhat urinous taste; the first two are energetic solvents of animal matter; and the three combine with oils, so as to form soaps. They unite with water in every proportion, and also with alcohol; and the first three combine with water after being carbonated.

ALKALIMETER. An instrument for measuring the alkaline force or purity of any of the alkalis of commerce. It is founded on the principle, that the quantity of real alkali present in any sample, is proportional to the quantity of acid which a given weight of it can neutralize. See the individual alkalis,Potash, andSoda.

ALKANA, is the name of the root and leaves ofLausania inermis, which have been long employed in the East, to dye the nails, teeth, hair, garments, &c. The leaves, ground and mixed with a little limewater, serve for dyeing the tails of horses in Persia and Turkey.

ALKANET, the root of. (Anchusa tinctoria.) A species of bugloss, cultivated chiefly in the neighbourhood of Montpellier. It affords a fine red colour to alcohol and oils; but a dirty red to water. Its principal use is for colouring ointments, cheeses, andpommades. The spirituous tincture gives to white marble a beautiful deep stain.

ALLIGATION. An arithmetical formula, useful, on many occasions, for ascertaining the proportion of constituents in a mixture, when they have undergone no change of volume by chemical action. When alcoholic liquors are mixed with water, there is a condensation of bulk, which renders that arithmetical rule inapplicable. The same thing holds, in some measure, in the union of metals by fusion. SeeAlloy.

ALLOY. (Alliage, Fr.;Legirung, Germ.) This term formerly signified a compound of gold and silver, with some metal of inferior value, but it now means any compound of any two or more metals whatever. Thus, bronze is an alloy of copper and tin; brass, an alloy of copper and zinc; and type metal, an alloy of lead and antimony. All the alloys possess metallic lustre, even when cut or broken to pieces; they are opaque; are excellent conductors of heat and electricity; are frequently susceptible of crystallising; are more or less ductile, malleable, elastic, and sonorous. An alloy which consists of metals differently fusible is usually malleable in the cold, and brittle when hot, as is exemplified with brass and gong metal.Many alloys consist of definite or equivalent proportions of the simple component metals, though some alloys seem to form in any proportion, like combinations of salt or sugar with water. It is probable that peculiar properties belong to the equivalent or atomic ratio, as is exemplified in the superior quality of brass made in that proportion.One metal does not alloy indifferently with every other metal, but it is governed in this respect by peculiar affinities; thus, silver will hardly unite with iron, but it combines readily with gold, copper, and lead. In comparing the alloys with their constituent metals, the following differences may be noted; in general, the ductility of the alloy is less than that of the separate metals, and sometimes in a very remarkable degree; on the contrary, the alloy is usually harder than the mean hardness of its constituents. The mercurial alloys or amalgams are, perhaps, exceptions to this rule.The specific gravity is rarely the mean between that of each of its constituents, but is sometimes greater and sometimes less, indicating, in the former case, an approximation, and in the latter, a recedure, of the particles from each other in the act of their union. The following tables of binary alloys exhibit this circumstance in experimental detail:—Alloys having a density greater thanthe mean of their constituents.Alloys having a density less thanthe mean of their constituents.Gold and zincGold and silverGold and tinGold and ironGold and bismuthGold and leadGold and antimonyGold and copperGold and cobaltGold and iridiumSilver and zincGold and nickelSilver and leadSilver and copperSilver and tinSilver and leadSilver and bismuthIron and bismuthSilver and antimonyIron and antimonyCopper and zincIron and leadCopper and tinTin and leadCopper and palladiumTin and palladiumCopper and bismuthTin and antimonyLead and antimonyNickel and arsenicPlatinum and molybdenumZinc and antimony.Palladium and bismuth.It would be hardly possible to infer the melting point of an alloy from that of each of its constituent metals; but, in general, the fusibility is increased by mutual affinity in their state of combination. Of this, a remarkable instance is afforded in the fusible metal consisting of 8 parts of bismuth, 5 of lead, and 3 of tin, which melts at theheat of boiling water or 212° Fahr., though the melting point deduced from the mean of its components should be 514°. This alloy may be rendered still more fusible by adding a very little mercury to it, when it forms an excellent material for certain anatomical injections, and for filling the hollows of carious teeth. Nor do the colours of alloys depend, in any considerable degree, upon those of the separate metals; thus, the colour of copper, instead of being rendered paler by a large addition of zinc, is thereby converted into the rich-looking pinchbeck metal.By means of alloys, we multiply, as it were, the numbers of useful metals, and sometimes give usefulness to such as are separately of little value. Since these compounds can be formed only by fusion, and since many metals are apt to oxidise readily at their melting temperature, proper precautions must be taken in making alloys to prevent this occurrence, which is incompatible with their formation. Thus, in combining tin and lead, rosin or grease is usually put on the surface of the melting metals, the carbon produced by the decomposition of which protects them, in most cases, sufficiently from oxidisement. When we wish to combine tin with iron, as in the tinning of cast-iron tea kettles, we rub sal ammoniac upon the surfaces of the hot metals in contact with each other, and thus exclude the atmospheric oxygen by means of its fumes. When there is a notable difference in the specific gravities of the metals which we wish to combine, we often find great difficulties in obtaining homogeneous alloys; for each metal may tend to assume the level due to its density, as is remarkably exemplified in alloys of gold and silver made without adequate stirring of the melting metals. If the mass be large, and slow of cooling after it is cast in an upright cylindrical form, the metals sometimes separate, to a certain degree, in the order of their densities. Thus, in casting large bells and cannons with copper alloys, the bottom of the casting is apt to contain too much copper and the top too much tin, unless very dexterous manipulation in mixing the fused materials have been employed immediately before the instant of pouring out the melted mass. When such inequalities are observed, the objects are broken and re-melted, after which they form a much more homogeneous alloy. This artifice of a double melting is often had recourse to, and especially in casting the alloys for the specula of telescopes.When we wish to alloy three or more metals, we often experience difficulties, either because one of the metals is more oxidable, or denser, or more fusible, than the others, or because there is no direct affinity between two of the metals. In the latter predicament, we shall succeed better by combining the three metals, first in pairs, for example, and then melting the two pairs together. Thus, it is difficult to unite iron with bronze directly; but if, instead of iron, we use tin plate, we shall immediately succeed, and the bronze, in this manner, acquires valuable qualities from the iron. Thus, also, to render brass better adapted for certain purposes, a small quantity of lead ought to be added to it, but this cannot be done directly with advantage: it is better to melt the lead first along with the zinc, and then to add this alloy to the melting copper, or the copper to that alloy, and fuse them together.We have said that the difference of fusibility was often an obstacle to metallic combination; but this circumstance may also be turned to advantage in decomposing certain alloys by the process calledeliquation. By this means silver may be separated from copper, if a considerable quantity of lead be first alloyed with the said copper; this alloy is next exposed to a heat just sufficient to melt the lead, which then sweats out, so to speak, from the pores of the copper, and carries along with it the greater part of the silver, for which it has a strong affinity. The lead and the silver are afterwards separated from each other, in virtue of their very different oxidability, by the action of heat and air.One of the alloys most useful to the arts is brass; it is more ductile and less easily oxidised than even its copper constituent, notwithstanding the opposite nature of the zinc. This alloy may exist in many different proportions, under which it has different names, as tombac, similor, pinchbeck, &c. Copper and tin form, also, a compound of remarkable utility, known under the names of hard brass, for the bushes, steps, and bearings of the axles, arbours, and spindles in machinery; and of bronze, bell-metal, &c. Gold and silver, in their pure state, are too soft and flexible to form either vessels or coins of sufficient strength and durability; but when alloyed with a little copper, they acquire the requisite hardness and stiffness for these and other purposes.When we have occasion to unite several pieces of the same or of different metals, we employ the process calledsoldering, which consists in fixing together the surfaces by means of an interposed alloy, which must be necessarily more fusible than the metal or metals to be joined. That alloy must also consist of metals which possess a strong affinity for the substances to be soldered together. Hence each metal would seem to require a particular kind of solder, which is, to a certain extent, true. Thus, the solder for gold trinkets and plate is an alloy of gold and silver, or gold and copper; that of silver trinkets, is an alloy of silver and copper; that of copper is either fine tin, for pieces that must not be exposed to the fire, or a brassy alloy called hard solder, of whichthe zinc forms a considerable proportion. The solder of lead and tinplate is an alloy of lead and tin, and that of tin is the same alloy with a little bismuth. Tinning, gilding, and silvering may also be reckoned a species of alloys, since the tin, gold, and silver are superficially united in these cases to other metals.Metallic alloys possess usually more tenacity than could be inferred from their constituents; thus, an alloy of twelve parts of lead with one of zinc has a tenacity double that of zinc. Metallic alloys are much more easily oxidised than the separate metals, a phenomenon which may be ascribed to the increase of affinity for oxygen which results from the tendency of the one of the oxides to combine with the other. An alloy of tin and lead heated to redness takes fire, and continues to burn for some time like a piece of bad turf.Every alloy is, in reference to the arts and manufactures, a new metal, on account of its chemical and physical properties. A vast field here remains to be explored. Not above sixty alloys have been studied by the chemists out of many hundred which may be made; and of these very few have yet been practically employed. Very slight modifications often constitute very valuable improvements upon metallic bodies. Thus, the brass most esteemed by turners at the lathe contains from two to three per cent. of lead; but such brass does not work well under the hammer; and, reciprocally, the brass which is best under the hammer is too tough for turning.That metallic alloys tend to be formed in definite proportions of their constituents is clear from the circumstance that the native gold of the auriferous sands is an alloy with silver, in the ratios of 1 atom of silver united to 4, 5, 6, 12 atoms of gold, but never with a fractional part of an atom. Also, in making an amalgam of 1 part of silver with 12 or 15 of mercury, and afterwards squeezing the mixture through chamois leather, the amalgam separates into 2 parts: one, containing a small proportion of silver and much mercury, passes through the skin; and the other, formed of 1 of silver and 8 of mercury, is a compound in definite proportions, which crystallises readily, and remains in the knot of the bag. An analogous separation takes place in the tinning of mirrors; for on loading them with the weights, a liquid amalgam of tin is squeezed out, while another amalgam remains in a solid form composed of tin and mercury in uniform atomic proportions. But, as alloys are generally soluble, so to speak, in each other, this definiteness of combination is masked and disappears in most cases.M. Chaudet has made some experiments on the means of detecting the metals of alloys by the cupelling furnace, and they promise useful applications. The testing depends upon the appearances exhibited by the metals and their alloys when heated on a cupel. Pure tin, when heated this way, fuses, becomes of a greyish black colour, fumes a little, exhibits incandescent points on its surface, and leaves an oxide, which, when withdrawn from the fire, is at first lemon-yellow, but when cold, white. Antimony melts, preserves its brilliancy, fumes, and leaves the vessel coloured lemon-yellow when hot, but colourless when cold, except a few spots of a rose tint. Zinc burns brilliantly, forming a cone of oxide; and the oxide, much increased in volume, is, when hot, greenish, but when cold, perfectly white. Bismuth fumes, becomes covered with a coat of melted oxide, part of which sublimes, and the rest enters the pores of the cupel; when cold, the cupel is of a fine yellow colour, with spots of a greenish hue. Lead resembles bismuth very much; the cold cupel is of a lemon-yellow colour. Copper melts, and becomes covered with a coat of black oxide; sometimes spots of a rose tint remain on the cupel.Alloys.—Tin 75, antimony 25, melt, become covered with a coat of black oxide, have very few incandescent points; when cold, the oxide is nearly black, in consequence of the action of the antimony: a1⁄400part of antimony may be ascertained in this way in the alloy. An alloy of antimony, containing tin, leaves oxide of tin in the cupel: a1⁄100part of tin may be detected in this way. An alloy of tin and zinc gives an oxide which, whilst hot, is of a green tint, and resembles philosophic wool in appearance. An alloy containing 99 tin, 1 zinc, did not present the incandescent points of pure tin, and gave an oxide of greenish tint when cold. Tin 95, bismuth 5 parts, gave an oxide of a grey colour. Tin and lead give an oxide of a rusty brown colour. An alloy of lead and tin, containing only 1 per cent. of the latter metal, when heated, does not expose a clean surface, like lead, but is covered at times with oxide of tin. Tin 75, and copper 25, did not melt, gave a black oxide: if the heat be much elevated, the under part of the oxide is white, and is oxide of tin; the upper is black, and comes from the copper. The cupel becomes of a rose colour. If the tin be impure from iron, the oxide produced by it is marked with spots of a rust colour.The degree of affinity between metals may be in some measure estimated by the greater or less facility with which, when of different degrees of fusibility or volatility, they unite, or with which they can, after union, be separated by heat. The greater or less tendency to separate into differently proportioned alloys, by long-continued fusion, may also give some information upon this subject. Mr. Hatchett remarked, in hiselaborate researches on metallic alloys, that gold made standard with the usual precautions, by silver, copper, lead, antimony, &c., and then cast, after long fusion, into vertical bars, was by no means an uniform compound; but that the top of the bar, corresponding to the metal at the bottom of the crucible, contained the larger proportion of gold. Hence, for a more thorough combination, two red-hot crucibles should be employed, and the liquefied metals should be alternately poured from the one into the other. To prevent unnecessary oxidisement from the air, the crucibles should contain, besides the metal, a mixture of common salt and pounded charcoal. The metallic alloy should also be occasionally stirred up with a rod of pottery ware.The most direct evidence of a chemical change having been effected in alloys is, when the compound melts at a lower temperature than the mean of its ingredients. Iron, which is nearly infusible, acquires almost the fusibility of gold when alloyed with this precious metal. The analogy is here strong with the increase of solubility which salts acquire by mixture, as is exemplified in the difficulty of crystallising residuums of saline solutions, or mother waters, as they are called.In common cases the specific gravity affords a good criterion whereby to judge of the proportion of two metals in an alloy. But a very fallacious rule has been given in some respectable works for computing the specific gravity that should result from the alloying of given quantities of two metals of known densities, supposing no chemical condensation or expansion of volume to take place. Thus, it has been taught, that if gold and copper be united in equal weights, the computed specific gravity is merely the arithmetical mean between the numbers denoting the two specific gravities. Whereas, the specific gravity of any alloy must be computed by dividing the sum of the two weights by the sum of the two volumes, compared, for conveniency sake, to water reckoned unity. Or, in another form, the rule may be stated thus:—Multiply the sum of the weights into the products of the two specific-gravity numbers for a numerator; and multiply each specific gravity-number into the weight of the other body, and add the two products together for a denominator. The quotient obtained by dividing the said numerator by the denominator, is the truly computed mean specific gravity of the alloy. On comparing with that density, the density found by experiment, we shall see whether expansion or condensation of volume has attended the metallic combination. Gold having a specific gravity of 19·36, and copper of 8·87, when they are alloyed in equal weights, give, by the fallacious rule of the arithmetical mean of the densities19·36 + 8·872= 14·11; whereas the rightly computed mean density is only 12·16. It is evident that, on comparing the first result with experiment, we should be led to infer that there had been a prodigious condensation of volume, though expansion has actually taken place. Let W, w be the two weights; P, p the two specific gravities, then M, the mean specific gravity, is given by the formula—(W + w)PpPw + pW∴ 2Δ = -(P - p)2P + p=twice the error of the arithmetical mean; which is therefore always in excess.

Many alloys consist of definite or equivalent proportions of the simple component metals, though some alloys seem to form in any proportion, like combinations of salt or sugar with water. It is probable that peculiar properties belong to the equivalent or atomic ratio, as is exemplified in the superior quality of brass made in that proportion.

One metal does not alloy indifferently with every other metal, but it is governed in this respect by peculiar affinities; thus, silver will hardly unite with iron, but it combines readily with gold, copper, and lead. In comparing the alloys with their constituent metals, the following differences may be noted; in general, the ductility of the alloy is less than that of the separate metals, and sometimes in a very remarkable degree; on the contrary, the alloy is usually harder than the mean hardness of its constituents. The mercurial alloys or amalgams are, perhaps, exceptions to this rule.

The specific gravity is rarely the mean between that of each of its constituents, but is sometimes greater and sometimes less, indicating, in the former case, an approximation, and in the latter, a recedure, of the particles from each other in the act of their union. The following tables of binary alloys exhibit this circumstance in experimental detail:—

It would be hardly possible to infer the melting point of an alloy from that of each of its constituent metals; but, in general, the fusibility is increased by mutual affinity in their state of combination. Of this, a remarkable instance is afforded in the fusible metal consisting of 8 parts of bismuth, 5 of lead, and 3 of tin, which melts at theheat of boiling water or 212° Fahr., though the melting point deduced from the mean of its components should be 514°. This alloy may be rendered still more fusible by adding a very little mercury to it, when it forms an excellent material for certain anatomical injections, and for filling the hollows of carious teeth. Nor do the colours of alloys depend, in any considerable degree, upon those of the separate metals; thus, the colour of copper, instead of being rendered paler by a large addition of zinc, is thereby converted into the rich-looking pinchbeck metal.

By means of alloys, we multiply, as it were, the numbers of useful metals, and sometimes give usefulness to such as are separately of little value. Since these compounds can be formed only by fusion, and since many metals are apt to oxidise readily at their melting temperature, proper precautions must be taken in making alloys to prevent this occurrence, which is incompatible with their formation. Thus, in combining tin and lead, rosin or grease is usually put on the surface of the melting metals, the carbon produced by the decomposition of which protects them, in most cases, sufficiently from oxidisement. When we wish to combine tin with iron, as in the tinning of cast-iron tea kettles, we rub sal ammoniac upon the surfaces of the hot metals in contact with each other, and thus exclude the atmospheric oxygen by means of its fumes. When there is a notable difference in the specific gravities of the metals which we wish to combine, we often find great difficulties in obtaining homogeneous alloys; for each metal may tend to assume the level due to its density, as is remarkably exemplified in alloys of gold and silver made without adequate stirring of the melting metals. If the mass be large, and slow of cooling after it is cast in an upright cylindrical form, the metals sometimes separate, to a certain degree, in the order of their densities. Thus, in casting large bells and cannons with copper alloys, the bottom of the casting is apt to contain too much copper and the top too much tin, unless very dexterous manipulation in mixing the fused materials have been employed immediately before the instant of pouring out the melted mass. When such inequalities are observed, the objects are broken and re-melted, after which they form a much more homogeneous alloy. This artifice of a double melting is often had recourse to, and especially in casting the alloys for the specula of telescopes.

When we wish to alloy three or more metals, we often experience difficulties, either because one of the metals is more oxidable, or denser, or more fusible, than the others, or because there is no direct affinity between two of the metals. In the latter predicament, we shall succeed better by combining the three metals, first in pairs, for example, and then melting the two pairs together. Thus, it is difficult to unite iron with bronze directly; but if, instead of iron, we use tin plate, we shall immediately succeed, and the bronze, in this manner, acquires valuable qualities from the iron. Thus, also, to render brass better adapted for certain purposes, a small quantity of lead ought to be added to it, but this cannot be done directly with advantage: it is better to melt the lead first along with the zinc, and then to add this alloy to the melting copper, or the copper to that alloy, and fuse them together.

We have said that the difference of fusibility was often an obstacle to metallic combination; but this circumstance may also be turned to advantage in decomposing certain alloys by the process calledeliquation. By this means silver may be separated from copper, if a considerable quantity of lead be first alloyed with the said copper; this alloy is next exposed to a heat just sufficient to melt the lead, which then sweats out, so to speak, from the pores of the copper, and carries along with it the greater part of the silver, for which it has a strong affinity. The lead and the silver are afterwards separated from each other, in virtue of their very different oxidability, by the action of heat and air.

One of the alloys most useful to the arts is brass; it is more ductile and less easily oxidised than even its copper constituent, notwithstanding the opposite nature of the zinc. This alloy may exist in many different proportions, under which it has different names, as tombac, similor, pinchbeck, &c. Copper and tin form, also, a compound of remarkable utility, known under the names of hard brass, for the bushes, steps, and bearings of the axles, arbours, and spindles in machinery; and of bronze, bell-metal, &c. Gold and silver, in their pure state, are too soft and flexible to form either vessels or coins of sufficient strength and durability; but when alloyed with a little copper, they acquire the requisite hardness and stiffness for these and other purposes.

When we have occasion to unite several pieces of the same or of different metals, we employ the process calledsoldering, which consists in fixing together the surfaces by means of an interposed alloy, which must be necessarily more fusible than the metal or metals to be joined. That alloy must also consist of metals which possess a strong affinity for the substances to be soldered together. Hence each metal would seem to require a particular kind of solder, which is, to a certain extent, true. Thus, the solder for gold trinkets and plate is an alloy of gold and silver, or gold and copper; that of silver trinkets, is an alloy of silver and copper; that of copper is either fine tin, for pieces that must not be exposed to the fire, or a brassy alloy called hard solder, of whichthe zinc forms a considerable proportion. The solder of lead and tinplate is an alloy of lead and tin, and that of tin is the same alloy with a little bismuth. Tinning, gilding, and silvering may also be reckoned a species of alloys, since the tin, gold, and silver are superficially united in these cases to other metals.

Metallic alloys possess usually more tenacity than could be inferred from their constituents; thus, an alloy of twelve parts of lead with one of zinc has a tenacity double that of zinc. Metallic alloys are much more easily oxidised than the separate metals, a phenomenon which may be ascribed to the increase of affinity for oxygen which results from the tendency of the one of the oxides to combine with the other. An alloy of tin and lead heated to redness takes fire, and continues to burn for some time like a piece of bad turf.

Every alloy is, in reference to the arts and manufactures, a new metal, on account of its chemical and physical properties. A vast field here remains to be explored. Not above sixty alloys have been studied by the chemists out of many hundred which may be made; and of these very few have yet been practically employed. Very slight modifications often constitute very valuable improvements upon metallic bodies. Thus, the brass most esteemed by turners at the lathe contains from two to three per cent. of lead; but such brass does not work well under the hammer; and, reciprocally, the brass which is best under the hammer is too tough for turning.

That metallic alloys tend to be formed in definite proportions of their constituents is clear from the circumstance that the native gold of the auriferous sands is an alloy with silver, in the ratios of 1 atom of silver united to 4, 5, 6, 12 atoms of gold, but never with a fractional part of an atom. Also, in making an amalgam of 1 part of silver with 12 or 15 of mercury, and afterwards squeezing the mixture through chamois leather, the amalgam separates into 2 parts: one, containing a small proportion of silver and much mercury, passes through the skin; and the other, formed of 1 of silver and 8 of mercury, is a compound in definite proportions, which crystallises readily, and remains in the knot of the bag. An analogous separation takes place in the tinning of mirrors; for on loading them with the weights, a liquid amalgam of tin is squeezed out, while another amalgam remains in a solid form composed of tin and mercury in uniform atomic proportions. But, as alloys are generally soluble, so to speak, in each other, this definiteness of combination is masked and disappears in most cases.

M. Chaudet has made some experiments on the means of detecting the metals of alloys by the cupelling furnace, and they promise useful applications. The testing depends upon the appearances exhibited by the metals and their alloys when heated on a cupel. Pure tin, when heated this way, fuses, becomes of a greyish black colour, fumes a little, exhibits incandescent points on its surface, and leaves an oxide, which, when withdrawn from the fire, is at first lemon-yellow, but when cold, white. Antimony melts, preserves its brilliancy, fumes, and leaves the vessel coloured lemon-yellow when hot, but colourless when cold, except a few spots of a rose tint. Zinc burns brilliantly, forming a cone of oxide; and the oxide, much increased in volume, is, when hot, greenish, but when cold, perfectly white. Bismuth fumes, becomes covered with a coat of melted oxide, part of which sublimes, and the rest enters the pores of the cupel; when cold, the cupel is of a fine yellow colour, with spots of a greenish hue. Lead resembles bismuth very much; the cold cupel is of a lemon-yellow colour. Copper melts, and becomes covered with a coat of black oxide; sometimes spots of a rose tint remain on the cupel.

Alloys.—Tin 75, antimony 25, melt, become covered with a coat of black oxide, have very few incandescent points; when cold, the oxide is nearly black, in consequence of the action of the antimony: a1⁄400part of antimony may be ascertained in this way in the alloy. An alloy of antimony, containing tin, leaves oxide of tin in the cupel: a1⁄100part of tin may be detected in this way. An alloy of tin and zinc gives an oxide which, whilst hot, is of a green tint, and resembles philosophic wool in appearance. An alloy containing 99 tin, 1 zinc, did not present the incandescent points of pure tin, and gave an oxide of greenish tint when cold. Tin 95, bismuth 5 parts, gave an oxide of a grey colour. Tin and lead give an oxide of a rusty brown colour. An alloy of lead and tin, containing only 1 per cent. of the latter metal, when heated, does not expose a clean surface, like lead, but is covered at times with oxide of tin. Tin 75, and copper 25, did not melt, gave a black oxide: if the heat be much elevated, the under part of the oxide is white, and is oxide of tin; the upper is black, and comes from the copper. The cupel becomes of a rose colour. If the tin be impure from iron, the oxide produced by it is marked with spots of a rust colour.

The degree of affinity between metals may be in some measure estimated by the greater or less facility with which, when of different degrees of fusibility or volatility, they unite, or with which they can, after union, be separated by heat. The greater or less tendency to separate into differently proportioned alloys, by long-continued fusion, may also give some information upon this subject. Mr. Hatchett remarked, in hiselaborate researches on metallic alloys, that gold made standard with the usual precautions, by silver, copper, lead, antimony, &c., and then cast, after long fusion, into vertical bars, was by no means an uniform compound; but that the top of the bar, corresponding to the metal at the bottom of the crucible, contained the larger proportion of gold. Hence, for a more thorough combination, two red-hot crucibles should be employed, and the liquefied metals should be alternately poured from the one into the other. To prevent unnecessary oxidisement from the air, the crucibles should contain, besides the metal, a mixture of common salt and pounded charcoal. The metallic alloy should also be occasionally stirred up with a rod of pottery ware.

The most direct evidence of a chemical change having been effected in alloys is, when the compound melts at a lower temperature than the mean of its ingredients. Iron, which is nearly infusible, acquires almost the fusibility of gold when alloyed with this precious metal. The analogy is here strong with the increase of solubility which salts acquire by mixture, as is exemplified in the difficulty of crystallising residuums of saline solutions, or mother waters, as they are called.

In common cases the specific gravity affords a good criterion whereby to judge of the proportion of two metals in an alloy. But a very fallacious rule has been given in some respectable works for computing the specific gravity that should result from the alloying of given quantities of two metals of known densities, supposing no chemical condensation or expansion of volume to take place. Thus, it has been taught, that if gold and copper be united in equal weights, the computed specific gravity is merely the arithmetical mean between the numbers denoting the two specific gravities. Whereas, the specific gravity of any alloy must be computed by dividing the sum of the two weights by the sum of the two volumes, compared, for conveniency sake, to water reckoned unity. Or, in another form, the rule may be stated thus:—Multiply the sum of the weights into the products of the two specific-gravity numbers for a numerator; and multiply each specific gravity-number into the weight of the other body, and add the two products together for a denominator. The quotient obtained by dividing the said numerator by the denominator, is the truly computed mean specific gravity of the alloy. On comparing with that density, the density found by experiment, we shall see whether expansion or condensation of volume has attended the metallic combination. Gold having a specific gravity of 19·36, and copper of 8·87, when they are alloyed in equal weights, give, by the fallacious rule of the arithmetical mean of the densities19·36 + 8·872= 14·11; whereas the rightly computed mean density is only 12·16. It is evident that, on comparing the first result with experiment, we should be led to infer that there had been a prodigious condensation of volume, though expansion has actually taken place. Let W, w be the two weights; P, p the two specific gravities, then M, the mean specific gravity, is given by the formula—

(W + w)PpPw + pW∴ 2Δ = -(P - p)2P + p=

twice the error of the arithmetical mean; which is therefore always in excess.

ALMOND. (Amande, Fr.;Mandel, Germ.) There are two kinds of almond which do not differ in chemical composition, only that the bitter, by some mysterious reaction of its constituents, generates in the act of distillation a quantity of a volatile oil, which contains hydrocyanic acid. Vogel obtained from bitter almonds 8·5 per cent. of husks. After pounding the kernels, and heating them to coagulate the albumen, he procured, by expression, 28 parts of an unctuous oil, which did not contain the smallest particle of hydrocyanic acid. The whole of the oil could not be extracted in this way. The expressed mass, treated with boiling water, afforded sugar and gum, and, in consequence of the heat, some of that acid. The sugar constitutes 6·5 per cent. and the gum 3. The vegetable albumen extracted, by means of caustic potash, amounted to 30 parts: the vegetable fibre to only 5. The poisonous aromatic oil, according to Robiquet and Boutron-Charlard, does not exist ready-formed in the bitter almond, but seems to be produced under the influence of ebullition with water. These chemists have shown that bitter almonds deprived of their unctuous oil by the press, when treated first by alcohol, and then by water, afford to neither of these liquids any volatile oil. But alcohol dissolves out a peculiar white crystalline body, without smell, of a sweetish taste at first, and afterwards bitter, to which they gave the name ofamygdaline. This substance does not seem convertible into volatile oil.Sweet almonds by the analysis of Boullay, consist of 54 parts of the bland almond oil, 6 of uncrystallisable sugar, 3 of gum, 24 of vegetable albumen, 24 of woody fibre, 5 of husks, 3·5 of water, 0·5 of acetic acid, including loss. We thus see that sweet almonds contain nearly twice as much oil as bitter almonds do.

Sweet almonds by the analysis of Boullay, consist of 54 parts of the bland almond oil, 6 of uncrystallisable sugar, 3 of gum, 24 of vegetable albumen, 24 of woody fibre, 5 of husks, 3·5 of water, 0·5 of acetic acid, including loss. We thus see that sweet almonds contain nearly twice as much oil as bitter almonds do.

ALMOND OIL. A bland fixed oil, obtained usually from bitter almonds by the action of a hydraulic press, either in the cold, or aided by hot iron plates. SeeOil.

ALOE. A series of trials has been made within a few years at Paris to ascertain the comparative strength of cables made of hemp and of the aloe from Algiers; and they are said to have all turned to the advantage of the aloe. Of cables of equal size, that made of aloe raised a weight of 2,000 kilogrammes (2 tons nearly); that made of hemp, a weight of only 400 kilogrammes. At the exposition of objects of national industry, two years ago, in Brussels, I saw aloe cordage placarded, as being far preferable to hempen. SeeRope.

ALUDEL. A pear-shaped vessel open at either end, of which a series are joined for distilling mercury in Spain. SeeMercury.

ALUM. (Alun, Fr.;Alaum, Germ.) A saline body, consisting of the earth of clay, called alumina by the chemists, combined with sulphuric acid and potash, or sulphuric acid and ammonia, into a triple compound. It occurs in the crystallised form of octahedrons, has an acerb subacid taste, and reddens the blue colour of litmus or red cabbage.Alum works existed many centuries ago at Roccha, formerly called Edessa, in Syria, whence the ancient name of Roch alum given to this salt. It was afterwards made at Foya Nova, near Smyrna, and in the neighbourhood of Constantinople. The Genoese, and other trading people of Italy, imported alum from these places into western Europe, for the use of the dyers of red cloth. About the middle of the fifteenth century, alum began to be manufactured at La Tolfa, Viterbo, and Volaterra, in Italy; after which time the importation of oriental alum was prohibited by the pope, as detrimental to the interests of his dominions. The manufacture of this salt was extended to Germany at the beginning of the sixteenth century, and to England at a somewhat later period, by Sir Thomas Chaloner, in the reign of Elizabeth. In its pure state, it does not seem to have been known to the ancients; for Pliny, in speaking of something like plumose alum, says, that it struck a black colour with pomegranate juice, which shows that the green vitriol was not separated from it. Thestypteriaof Dioscorides, and thealumenof Pliny, comprehended, apparently, a variety of saline substances, of which sulphate of iron, as well as alumina, was probably a constituent part. Pliny, indeed, says, that a substance called in Greek Ὑγρα, or watery, probably from its very soluble nature, which was milk-white, was used for dyeing wool of bright colours. This may have been the mountain butter of the German mineralogists, which is a native sulphate of alumina, of a soft texture, waxy lustre, and unctuous to the touch.The only alum manufactories now worked in Great Britain, are those of Whitby, in England, and of Hurlett and Campsie, near Glasgow, in Scotland; and these derive the acid and earthy constituents of the salt from a mineral called alum slate. This mineral has a bluish or greenish-black colour, emits sulphurous fumes when heated, and acquires thereby an aluminous taste. The alum manufactured in Great Britain contains potash as its alkaline constituent; that made in France contains, commonly, ammonia, either alone, or with variable quantities of potash. Alum may in general be examined by water of ammonia, which separates from its watery solutions its earthy basis, in the form of a light flocculent precipitate. If the solution be dilute, this precipitate will float long as an opalescent cloud.If we dissolve alum in 20 parts of water, and drop this solution slowly into water or caustic ammonia till this be nearly, but not entirely, saturated, a bulky white precipitate will fall down, which, when properly washed with water, is pure aluminous earth or clay, and dried forms 10·82 per cent. of the weight of the alum. If this earth, while still moist, be dissolved in dilute sulphuric acid, it will constitute, when as neutral as possible, the sulphate of alumina, which requires only two parts of cold water for its solution. If we now decompose this solution, by pouring into it water of ammonia, there appears an insoluble white powder, which is subsulphate of alumina, or basic alum; and contains three times as much earth as exists in the neutral sulphate. If, however, we pour into the solution of the neutral sulphate of alumina a solution of sulphate of potash, a white powder will fall if the solutions be concentrated, which is truealum; but if the solutions be dilute, by evaporating their mixture, and cooling it, crystals of alum will be obtained.When newly precipitated alumina is boiled in a solution of alum, a portion of the earth enters into combination with the salt, constituting an insoluble compound, which falls in the form of a white powder. The same combination takes place, if we decompose a boiling hot solution of alum with a solution of potash, till the mixture appears nearly neutral by litmus paper. This insoluble or basic alum exists native in the alum-stone of Tolfa, near Civita Vecchia, and it consists in 100 parts of 19·72 parts of sulphate of potash, 61·99 basic sulphate of alumina, and 18·29 water. When this mineral is treated with a due quantity of sulphuric acid, it dissolves, and is converted into the crystallisable alum of commerce.These experimental facts develope the principles of the manufacture of alum, which is prosecuted under various modifications, for its important uses in the arts. Alum seldom occurs ready-formed in nature; occasionally, as an efflorescence on stones, and incertain mineral waters in the East Indies. The alum of European commerce is fabricated artificially, either from the alum schists or stones, or from clay. The mode of manufacture differs according to the nature of these earthy compounds. Some of them, such as the alum stone, contain all the elements of the salt, but mixed with other matters, from which it must be freed. The schists contain only the elements of two of the constituents, namely, clay and sulphur, which are convertible into sulphate of alumina, and this may be then made into alum by adding the alkaline ingredient. To this class belong the alum slates, and other analogous schists, containing brown coal.1.Manufacture of Alum from the Alum Stone.—The alum-stone is a rare mineral, being found in moderate quantity at Tolfa, and in larger in Hungary, at Bereghszasz, and Muszag, where it forms entire beds in a hard substance, partly characterised by numerous cavities, containing drusy crystallisations of alum-stone or basic alum. The larger lumps contain more or fewer flints disseminated through them, and are, according to their quality, either picked out to make alum, or are thrown away. The sorted pieces are roasted or calcined, by which operation apparently the hydrate of alumina, associated with the sulphate of alumina, loses its water, and, as burnt clay, loses its affinity for alum. It becomes, therefore, free; and during the subsequent exposure to the weather the stone gets disintegrated, and the alum becomes soluble in water.The calcination is performed in common lime-kilns in the ordinary way. In the regulation of the fire it is requisite, here, as with gypsum, to prevent any fusion or running together of the stones, or even any disengagement of sulphuric or sulphurous acids, which would cause a corresponding defalcation in the product of alum. For this reason the contact of the ignited stones with carbonaceous matter ought to be avoided.The calcined alum-stones, piled in heaps from 2 to 3 feet high, are to be exposed to the weather, and meanwhile they must be continually kept moist by sprinkling them with water. As the water combines with the alum the stones crumble down, and fall, eventually, into a pasty mass, which must be lixiviated with warm water, and allowed to settle in a large cistern. The clear supernatant liquor, being drawn off, must be evaporated, and then crystallised. A second crystallisation finishes the process, and furnishes a marketable alum. Thus the Roman alum is made, which is covered with a fine red film of peroxide of iron.2.Alum Manufacture from Alum Schist.—The greater portion of the alum found in British commerce is made from alum-slate and analogous minerals. This slate contains more or less iron pyrites, mixed with coaly or bituminous matter, which is occasionally so abundant as to render them somewhat combustible. In the strata of brown coal and bituminous wood, where the upper layers lie immediately under clay beds, they consist of the coaly substance rendered impure with clay and pyrites. This triple mixture constitutes the essence of all good alum schists, and it operates spontaneously towards the production of sulphate of alumina. The coal serves to make the texture open, and to allow the air and moisture to penetrate freely, and to change the sulphur and iron present into acid and oxide. When these schists are exposed to a high temperature in contact with air, the pyrites loses one half of its sulphur, in the form of sublimed sulphur or sulphurous acid, and becomes a black sulphuret of iron, which speedily attracts oxygen, and changes to sulphate of iron, or green vitriol. The brown coal schists contain, commonly, some green vitriol crystals spontaneously formed in them. The sulphate of iron transfers its acid to the clay, progressively, as the iron, by the action of the air with a little elevation of temperature, becomes peroxidised; whereby sulphate of alumina is produced. A portion of the green vitriol remains, however, undecomposed, and so much the more as there may happen to be less of other salifiable bases present in the clay slate. Should a little magnesia or lime be present, the vitriol gets more completely decomposed, and a portion of Epsom salt and gypsum is produced.The manufacture of alum from alum schists may be distributed under the six following heads:—1. The preparation of the alum slate. 2. The lixiviation of the slate. 3. The evaporation of the lixivium. 4. The addition of the saline ingredients, or the precipitation of the alum. 5. The washing of the aluminous salts; and 6. The crystallisation.1.Preparation of the Alum Slate.—Some alum slates are of such a nature that, being piled in heaps in the open air, and moistened from time to time, they get spontaneously hot, and by degrees fall into a pulverulent mass, ready to be lixiviated. The greater part, however, require the process of ustulation, from which they derive many advantages. The cohesion of the dense slates is thereby so much impaired that their decomposition becomes more rapid; the decomposition of the pyrites is quickened by the expulsion of a portion of the sulphur; and the ready-formed green vitriol is partly decomposed by the heat, with a transference of its sulphuric acid to the clay, and the production of sulphate of alumina.Such alum-slates as contain too little bitumen or coal for the roasting process must be interstratified with layers of small coal or brushwood over an extensive surface. AtWhitby the alum rock, broken into small pieces, is laid upon a horizontal bed of fuel, composed of brushwood; but at Hurlett small coal is chiefly used for the lower bed. When about four feet of the rock is piled on, fire is set to the bottom in various parts; and whenever the mass is fairly kindled, more rock is placed over the top. At Whitby this piling process is continued till the calcining heap is raised to the height of 90 or 100 feet. The horizontal area is also augmented at the same time till it forms a great bed nearly 200 feet square, having therefore about 100,000 yards of solid measurement. The rapidity of the combustion is tempered by plastering up the crevices with small schist moistened. When such an immense mass is inflamed, the heat is sure to rise too high, and an immense waste of sulphur and sulphuric acid must ensue. This evil has been noticed at the Whitby works. At Hurlett the height to which the heap is piled is only a few feet, while the horizontal area is expanded; which is a much more judicious arrangement. At Whitby 130 tons of calcined schist produce on an average 1 ton of alum. In this humid climate it would be advisable to pile up on the top of the horizontal strata of brushwood or coal, and schist, a pyramidal mass of schist, which having its surface plastered smooth, with only a few air-holes, will protect the mass from the rains, and at the same time prevent the combustion from becoming too vehement. Should heavy rains supervene, a gutter must be scooped out round the pile for receiving the aluminous lixivium, and conducting it into the reservoir.It may be observed, that certain alum schists contain abundance of combustible matter, to keep up a suitable calcining heat after the fire is once kindled; and therefore nothing is needed but the first layer of brushwood, which, in this case, may be laid over the first bed of the bituminous schist.A continual, but very slow, heat, with a smothered fire, is most beneficial for the ustulation of alum slate. When the fire is too brisk, the sulphuret of iron may run with the earthy matters into a species of slag, or the sulphur will be dissipated in vapour, by both of which accidents the product of alum will be impaired. Those bituminous alum schists which have been used as fuel under steam boilers have suffered such a violent combustion that their ashes yield almost no alum. Even the best regulated calcining piles are apt to burn too briskly in high winds, and should have their draught-holes carefully stopped under such circumstances. It may be laid down as a general rule, that the slower the combustion the richer the roasted ore will be in sulphate of alumina. When the calcination is complete, the heap diminishes to one half its original bulk; it is covered with a light reddish ash, and is open and porous in the interior, so that the air can circulate freely throughout the mass. To favour this access of air, the masses should not be too lofty; and in dry weather a little water should be occasionally sprinkled on them, which, by dissolving away some of the saline matter, will make the interior more open to the atmosphere.When the calcined mineral becomes thoroughly cold, we may proceed to the lixiviation. But as, from the first construction of the piles or beds till their complete calcination, many weeks, or even months, may elapse, care ought to be taken to provide a sufficient number or extent of them, so as to have an adequate supply of material for carrying on the lixiviating and crystallising processes during the course of the year, or at least during the severity of the winter season, when the calcination may be suspended, and the lixiviation becomes unsatisfactory. The beds are known to be sufficiently decomposed by the efflorescence of the salt which appears upon the stones, from the strong aluminous taste of the ashes, and from the appropriate chemical test of lixiviating an aliquot average portion of the mass, and seeing how much alum it will yield to solution of muriate or sulphate of potash.2.The Lixiviation.—The lixiviation is best performed in stone-built cisterns; those of wood, however strong at first, are soon decomposed, and need repairs. They ought to be erected in the neighbourhood of the calcining heaps, to save the labour of transport, and so arranged that the solutions from the higher cisterns may spontaneously flow into the lower. In this point of view, a sloping terrace is the best situation for an alum work. In the lowest part of this terrace, and in the neighbourhood of the boiling-house, there ought to be two or more large deep tanks, for holding the crude lixivium, and they should be protected from the rain by a proper shed. Upon a somewhat higher level the cisterns of the clear lixivium may be placed. Into the highest range of cisterns the calcined mineral is to be put, taking care to lay the largest lumps at the bottom, and to cover them with lighter ashes. A sufficient quantity of water is now to be run over it, and allowed to rest for some time. The lixivium may then be drawn off, by a stopcock connected with a pipe at the bottom of the cistern, and run into another cistern at a somewhat lower level. Fresh water must now be poured on the partly exhausted schist, and allowed to remain for a sufficient time. This lixivium, being weak, should be run off into a separate tank. In some cases a third addition of fresh water may be requisite, and the weak lixivium which is drawn off may be reserved for a fresh portion of calcined mineral. In order to save evaporation, it is always requisite to strengthen weakleys by employing them instead of water for fresh portions of calcined schist. Upon the ingenious disposition and form of these lixiviating cisterns much of the economy and success of an alum work depend. The hydrometer should be always used to determine the degree of concentration which the solutions acquire.The lixiviated stone being thus exhausted of its soluble ingredients, is to be removed from the cisterns, and piled up in a heap in any convenient place, where it may be left either spontaneously to decompose, or, after drying, may be subjected to another calcination.The density of the solution may be brought, upon an average, up to the sp. gr. of from 1·09 to 1·15. The latter density may always be obtained by pumping up the weaker solutions upon fresh calcinedmine. This strong liquor is then drawn off, when the sulphate of lime, the oxide of iron, and the earths are deposited. It is of advantage to leave the liquor exposed for some time, whereby the green vitriol may pass into a persulphate of iron with the deposition of some oxide, while the liberated acid may combine with some of the clay present, so as to increase the quantity of sulphate of alumina. The manufacture of alum is the more imperfect, as the quantity of sulphate of iron left undecomposed is greater, and therefore every expedient ought to be tried to convert the sulphate of iron into sulphate of alumina.3.The evaporation of the Schist Lixivium.—As the aluminous liquors, however well settled at first, are apt, on the great scale, to deposit earthy matters in the course of their concentration by heat, they are best evaporated by a surface fire, such as that employed at Hurlett and Campsie. A water-tight stone cistern must be built, having a layer of well rammed clay behind the flags or tiles which line its bottom and sides. This cistern may be 4 or 6 feet wide, 2 or 3 feet deep, and 30 or 40 feet long, and it is covered in by an arch of stone or brickwork. At one extremity of this tunnel, or covered canal, a fire-grate is set, and at the other a lofty chimney is erected. The cistern being filled to the brim with the alum ley, a strong fire is kindled in the reverberatory grate, and the flame and hot air are forced to sweep along the surface of the liquor, so as to keep it in constant ebullition, and to carry off the aqueous parts in vapour. The soot which is condensed in the process falls to the bottom, and leaves the body of the liquor clear. As the concentration goes on, more of the rough lixivium is run in from the settling cistern, placed on a somewhat higher level, till the whole gets charged with a clear liquor of a specific gravity sufficiently high for transferring into the proper lead boilers.At Whitby, the lead pans are 10 feet long, 4 feet 9 inches wide, 2 feet 2 inches deep at the one end, and 2 feet 8 inches deep at the other. This increase of depth and corresponding slope, facilitates the decantation of the concentrated lixivium by means of a syphon, applied at the lower end. The bottom of the pan is supported by a series of parallel iron bars, placed very near each other. In these lead pans the liquor is concentrated, at a brisk boiling heat, by means of the flame of a flue beneath them. Every morning the pans are emptied into a settling cistern of stone or lead. The specific gravity of the liquor should be about 1·4 or 1·5, being a saturated solution of the saline matters present. The proper degree of density must vary, however, with different kinds of lixivia, and according to the different views of the manufacturer. For a liquor which consists of two parts of sulphate of alumina, and one part of sulphate of iron, a specific gravity of 1·25 may be sufficient; but for a solution which contains two parts of sulphate of iron to one of sulphate of alumina, so that the green vitriol must be withdrawn first of all by crystallisation, a specific gravity of 1·4 may be requisite.The construction of an evaporating furnace well adapted to the concentration of aluminous and other crude lixivia, is described underSoda. The liquor basin may be made of tiles or flags puddled in clay, and secured at the seams with a goodhydrauliccement. A mortar made of quicklime mixed with the exhausted schist in powder, and iron turnings, is said to answer well for this purpose. Sometimes over the reverberatory furnace a flat pan is laid, instead of the arched top, into which the crude liquor is put for neutralisation and partial concentration. In Germany, such a pan is made of copper, because iron would waste too fast, and lead would be apt to melt. From this preparation basin the under evaporating trough is gradually supplied with hot liquor. At one side of this lower trough, there is sometimes a door, through which the sediment may be raked out as it accumulates upon the bottom. Such a contrivance is convenient for this mode of evaporation, and it permits, also, any repairs to be readily made; but, indeed, an apparatus of this kind, well mounted at first, will serve for many years.In the course of the final concentration of the liquors, it is customary to add some of the mother waters of a former process, the quantity of which must be regulated by a proper analysis and knowledge of their contents. If these mother waters contain much free sulphuric acid, from the peroxidation of their sulphate of iron, they may prove useful in dissolving a portion of the alumina of the sediment which is always present in greater or less quantity.4.The precipitation of the Alum by adding Alkaline Salts.—As a general rule, it is most advantageous to separate, first of all, from the concentrated clear liquors, the alum in the state of powder or small crystals, by addition of the proper alkaline matter, and to leave the mingled foreign salts, such as the sulphate of iron or magnesia, in solution, instead of trying to abstract these salts by a previous crystallisation. In this way we not only simplify and accelerate the manufacture of alum, and leave the mother waters to be worked up at any convenient season, but we also avoid the risk of withdrawing any of the sulphate of alumina with the sulphate of iron or magnesia. On this account, the concentration of the liquor ought not to be pushed so far as that, when it gets cold, it should throw out crystals, but merely to the verge of this point. This density may be determined by suitable experiments.The clear liquor should now be run off into the precipitation cistern, and have the proper quantity of sulphate or muriate of potash, or impure sulphate or carbonate of ammonia added to it. The sulphate of potash, which is the best precipitant, forms 18·34 parts out of 100 of crystallised alum; and therefore that quantity of it, or its equivalent in muriate of potash, or other potash or ammoniacal salts, must be introduced into the aluminous liquor. Since sulphate of potash takes 10 parts of cold water to dissolve it, but is much more soluble in boiling water, and since the precipitation of alum is more abundant the more concentrated the mingled solutions are, it would be prudent to add the sulphate solution as hot as may be convenient; but, as muriate of potash is fully three times more soluble in cold water, it is to be preferred as a precipitant, when it can be procured at a cheap rate. It has, also, the advantage of decomposing the sulphate of iron present into a muriate, a salt very difficult of crystallisation, and, therefore, less apt to contaminate the crystals of alum. The quantity of alkaline salts requisite to precipitate the alum, in a granular powder, from the lixivium, depends on their richness in potash or ammonia, on the one hand, and on the richness of the liquors in sulphate of alumina on the other; and it must be ascertained, for each large quantity of product, by a preliminary experiment in a precipitation glass. Here, an aliquot measure of the aluminous liquor being taken, the liquid precipitant must be added in successive portions, as long as it causes any cloud, when the quantity added will be indicated by the graduation of the vessel. A very exact approximation is not practicable upon the great scale; but, as the mother waters are afterwards mixed together in one cistern, any excess of the precipitant, at one time, is corrected by excess of aluminous sulphate at another, and the resulting alum meal is collected at the bottom. When the precipitated saline powder is thoroughly settled and cooled, the supernatant mother water must be drawn off by a pump, or rather a syphon or stopcock, into a lower cistern. The more completely this drainage is effected, the more easily and completely will the alum be purified.This mother liquor has, generally, a specific gravity of 1·4 at a medium temperature of the atmosphere, and consists of a saturated solution of sulphate or muriate of black and red oxide of iron, with sulphate of magnesia, in certain localities, and muriate of soda, when the soaper’s salt has been used as a precipitant, as also a saturated solution of sulphate of alumina. By adding some of it, from time to time, to the fresh lixivia, a portion of that sulphate is converted into alum; but, eventually, the mother water must be evaporated, so as to obtain from it a crop of ferruginous crystals; after which it becomes capable, once more, of giving up its alum to the alkaline precipitants.When the aluminous lixivia contain a great deal of sulphate of iron, it may be good policy to withdraw a portion of it by crystallisation before precipitating the alum. With this view, the liquors must be evaporated to the density of 1·4, and then run off into crystallising stone cisterns. After the green vitriol has concreted, the liquor should be pumped back into the evaporating pan, and again brought to the density of 1·4. On adding to it, now, the alkaline precipitants, the alum will fall down from this concentrated solution, in a very minute crystalline powder, very easy to wash and purify. But this method requires more vessels and manipulation than the preceding, and should only be had recourse to from necessity; since it compels us to carry on the manufacture of both the valuable alum and the lower priced salts at the same time; moreover, the copperas extracted at first from the schist liquors carries with it, as we have said, a portion of the sulphate of alumina, and acquires thereby a dull aspect; whereas the copperas obtained after the separation of the alum is of a brilliant appearance.5.The washing, or edulcoration, of the Alum Powder.—This crystalline pulverulent matter has a brownish colour, from the admixture of the ferruginous liquors; but it may be freed from it by washing with very cold water, which dissolves not more than one sixteenth of its weight of alum. After stirring the powder and the water well together, the former must be allowed to settle, and then the washing must be drawn off. A second washing will render the alum nearly pure. The less water is employed, and the more effectually it is drained off, the more complete is the process. The second water may be used in the first washing of another portion ofalum powder, in the place of pure water. These washings may be added to the schist lixivia.6.The crystallisation.—The washed alum is put into a lead pan, with just enough water to dissolve it at a boiling heat; fire is applied, and the solution is promoted by stirring. Whenever it is dissolved in a saturated state, it is run off into the crystallising vessels, which are calledrochingcasks. These casks are about five feet high, three feet wide in the middle, somewhat narrower at the ends; they are made of very strong staves, nicely fitted to each other, and held together by strong iron hoops, which are driven onpro tempore, so that they may be easily knocked off again, in order to take the staves asunder. The concentrated solution, during its slow cooling in these close vessels, forms large regular crystals, which hang down from the top, and project from the sides, while a thick layer or cake lines the whole interior of the cask. At the end of eight or ten days, more or less, according to the weather, the hoops and staves are removed, when a cask of apparently solid alum is disclosed to view. The workman now pierces this mass with a pickaxe at the side near the bottom, and allows the mother water of the interior to run off on the sloping stone floor into a proper cistern, whence it is taken and added to another quantity of washed powder to be crystallised with it. The alum is next broken into lumps, exposed in a proper place to dry, and is then put into the finished bing for the market. There is sometimes a little insoluble basic alum (subsulphate) left at the bottom of the cask. This being mixed with the former mother liquors, gets sulphuric acid from them; or, being mixed with a little sulphuric acid, it is equally converted into alum.When, instead of potash or its salts, the ammoniacal salts are used, or putrid urine, with the aluminous lixivia, ammoniacal alum is produced, which is perfectly similar to the potash alum in its appearance and properties. At a gentle heat both lose their water of crystallisation, amounting to 451⁄2per cent. for the potash alum, and 48 for the ammoniacal. The quantity of acid is the same in both, as, also, very nearly the quantity of alumina, as the following analyses will show:Potash alum.Ammonia alum.Sulphate of potash18·34Sulphate of ammonia12·88Sulphate of alumina36·20Sulphate of alumina38·64Water45·46Water48·48100·00100·00Or otherwise, Potash alum.Ammonia alum.1 atom sulphate of potash1089·071 atom sulphate of ammonia716·71atom sulphate ofalumina2149·801atom sulphate ofalumina2149·824 water2669·5224 water2699·55938·395566·0Or, Potash alum.Ammonia alum.Alumina10·82Alumina11·90Potash9·94Ammonia3·89Sulphuric Acid33·77Sulphuric acid36·10Water45·47Water48·11100·00100·00When heated pretty strongly, the ammoniacal alum loses its sulphuric acid and ammonia, and only the earth remains. This is a very convenient process for procuring pure alumina. Ammoniacal alum is easily distinguished from the other by the smell of ammonia which it exhales when triturated with quicklime. The Roman alum, made from alum stone, possesses most of the properties of the schist-made alums, but it has a few peculiar characters: it crystallises always in opaque cubes, whereas the common alum crystallises in transparent octahedrons. It is probable that Roman alum is a sulphate of alumina and potash, with a slight excess of the earthy ingredient. It is permanent when dissolved in cold water; for after a slow evaporation it is recovered in a cubical form. But when it is dissolved in water heated to 110° Fahr. and upwards, or when its solution is heated above this pitch, subsulphate of alumina falls, and on evaporation octahedral crystals of common alum are obtained. The exact composition of the Roman alum has not been determined, as far as I know. It probably differs from the other also in its water of crystallisation. The Roman alum contains, according to MM. Thenard and Roard, only1⁄2200of sulphate of iron, while the common commercialalums contain1⁄1000. It may be easily purified by solution, granulation, crystallisation, and washing, as has been already explained.Alum is made extensively in France from an artificial sulphate of alumina. For this purpose clays are chosen as free as possible from carbonate of lime and oxide of iron. They are calcined in a reverberatory furnace, in order to expel the water, to peroxidise the iron, and to render the alumina more easily acted on by the acid. The expulsion of the water renders the clay porous and capable of absorbing the sulphuric acid by capillary attraction. The peroxidation of the iron renders it less soluble in the sulphuric acid; and the silica of the clay, by reacting on the alumina, impairs its aggregation, and makes it more readily attracted by the acid. The clay should, therefore, be moderately calcined; but not so as to indurate it like pottery ware, for it would then suffer a species of siliceous combination which would make it resist the action of acids. The clay is usually calcined in a reverberatory furnace, the flame of which serves thereafter to heat two evaporating pans and a basin for containing a mixture of the calcined clay and sulphuric acid. As soon as the clay has become friable in the furnace it is taken out, reduced to powder, and passed through a fine sieve. With 100 parts of the pulverised clay, 45 parts of sulphuric acid, of sp. gr. 1·45, are well mixed, in a stone basin, arched over with brickwork. The flame and hot air of a reverberatory furnace are made to play along the mixture, in the same way as described for evaporating the schist liquors. SeeSoda. The mixture, being stirred from time to time, is, at the end of a few days, to be raked out, and to be set aside in a warm place, for the acid to work on the clay, during six or eight weeks. At the end of this time it must be washed, to extract the sulphate of alumina. With this view, it may be treated like the roasted alum ores above described. If potash alum is to be formed, this sulphate of alumina is evaporated to the specific gravity of 1·38; but if ammonia alum, to the specific gravity of only 1·24; because the sulphate of ammonia, being soluble in twice its weight of water, will cause a precipitation of pulverulent alum from a weaker solution of sulphate of alumina than the less soluble sulphate of potash could do.The alum stone, from which the Roman alum is made, contains potash. The following analysis ofalunite, by M. Cordier, places this fact in a clear light:—Sulphate of potash18·53Sulphate of alumina38·50Hydrate of alumina42·97100·00To transform this compound into alum, it is merely necessary to abstract the hydrate of alumina. The ordinary alum stone, however, is rarely so pure as the above analysis would seem to show; for it contains a mixture of other substances; and the above are in different proportions.Alum is very extensively employed in the arts, most particularly in dyeing, lake making, dressing sheep-skins, pasting paper, in clarifying liquors, &c. Its purity for the dyer may be tested by prussiate of potash, which will give solution of alum a blue tint in a few minutes if it contain even a very minute portion of iron. A bit of nut-gall is also a good test of iron.

Alum works existed many centuries ago at Roccha, formerly called Edessa, in Syria, whence the ancient name of Roch alum given to this salt. It was afterwards made at Foya Nova, near Smyrna, and in the neighbourhood of Constantinople. The Genoese, and other trading people of Italy, imported alum from these places into western Europe, for the use of the dyers of red cloth. About the middle of the fifteenth century, alum began to be manufactured at La Tolfa, Viterbo, and Volaterra, in Italy; after which time the importation of oriental alum was prohibited by the pope, as detrimental to the interests of his dominions. The manufacture of this salt was extended to Germany at the beginning of the sixteenth century, and to England at a somewhat later period, by Sir Thomas Chaloner, in the reign of Elizabeth. In its pure state, it does not seem to have been known to the ancients; for Pliny, in speaking of something like plumose alum, says, that it struck a black colour with pomegranate juice, which shows that the green vitriol was not separated from it. Thestypteriaof Dioscorides, and thealumenof Pliny, comprehended, apparently, a variety of saline substances, of which sulphate of iron, as well as alumina, was probably a constituent part. Pliny, indeed, says, that a substance called in Greek Ὑγρα, or watery, probably from its very soluble nature, which was milk-white, was used for dyeing wool of bright colours. This may have been the mountain butter of the German mineralogists, which is a native sulphate of alumina, of a soft texture, waxy lustre, and unctuous to the touch.

The only alum manufactories now worked in Great Britain, are those of Whitby, in England, and of Hurlett and Campsie, near Glasgow, in Scotland; and these derive the acid and earthy constituents of the salt from a mineral called alum slate. This mineral has a bluish or greenish-black colour, emits sulphurous fumes when heated, and acquires thereby an aluminous taste. The alum manufactured in Great Britain contains potash as its alkaline constituent; that made in France contains, commonly, ammonia, either alone, or with variable quantities of potash. Alum may in general be examined by water of ammonia, which separates from its watery solutions its earthy basis, in the form of a light flocculent precipitate. If the solution be dilute, this precipitate will float long as an opalescent cloud.

If we dissolve alum in 20 parts of water, and drop this solution slowly into water or caustic ammonia till this be nearly, but not entirely, saturated, a bulky white precipitate will fall down, which, when properly washed with water, is pure aluminous earth or clay, and dried forms 10·82 per cent. of the weight of the alum. If this earth, while still moist, be dissolved in dilute sulphuric acid, it will constitute, when as neutral as possible, the sulphate of alumina, which requires only two parts of cold water for its solution. If we now decompose this solution, by pouring into it water of ammonia, there appears an insoluble white powder, which is subsulphate of alumina, or basic alum; and contains three times as much earth as exists in the neutral sulphate. If, however, we pour into the solution of the neutral sulphate of alumina a solution of sulphate of potash, a white powder will fall if the solutions be concentrated, which is truealum; but if the solutions be dilute, by evaporating their mixture, and cooling it, crystals of alum will be obtained.

When newly precipitated alumina is boiled in a solution of alum, a portion of the earth enters into combination with the salt, constituting an insoluble compound, which falls in the form of a white powder. The same combination takes place, if we decompose a boiling hot solution of alum with a solution of potash, till the mixture appears nearly neutral by litmus paper. This insoluble or basic alum exists native in the alum-stone of Tolfa, near Civita Vecchia, and it consists in 100 parts of 19·72 parts of sulphate of potash, 61·99 basic sulphate of alumina, and 18·29 water. When this mineral is treated with a due quantity of sulphuric acid, it dissolves, and is converted into the crystallisable alum of commerce.

These experimental facts develope the principles of the manufacture of alum, which is prosecuted under various modifications, for its important uses in the arts. Alum seldom occurs ready-formed in nature; occasionally, as an efflorescence on stones, and incertain mineral waters in the East Indies. The alum of European commerce is fabricated artificially, either from the alum schists or stones, or from clay. The mode of manufacture differs according to the nature of these earthy compounds. Some of them, such as the alum stone, contain all the elements of the salt, but mixed with other matters, from which it must be freed. The schists contain only the elements of two of the constituents, namely, clay and sulphur, which are convertible into sulphate of alumina, and this may be then made into alum by adding the alkaline ingredient. To this class belong the alum slates, and other analogous schists, containing brown coal.

1.Manufacture of Alum from the Alum Stone.—The alum-stone is a rare mineral, being found in moderate quantity at Tolfa, and in larger in Hungary, at Bereghszasz, and Muszag, where it forms entire beds in a hard substance, partly characterised by numerous cavities, containing drusy crystallisations of alum-stone or basic alum. The larger lumps contain more or fewer flints disseminated through them, and are, according to their quality, either picked out to make alum, or are thrown away. The sorted pieces are roasted or calcined, by which operation apparently the hydrate of alumina, associated with the sulphate of alumina, loses its water, and, as burnt clay, loses its affinity for alum. It becomes, therefore, free; and during the subsequent exposure to the weather the stone gets disintegrated, and the alum becomes soluble in water.

The calcination is performed in common lime-kilns in the ordinary way. In the regulation of the fire it is requisite, here, as with gypsum, to prevent any fusion or running together of the stones, or even any disengagement of sulphuric or sulphurous acids, which would cause a corresponding defalcation in the product of alum. For this reason the contact of the ignited stones with carbonaceous matter ought to be avoided.

The calcined alum-stones, piled in heaps from 2 to 3 feet high, are to be exposed to the weather, and meanwhile they must be continually kept moist by sprinkling them with water. As the water combines with the alum the stones crumble down, and fall, eventually, into a pasty mass, which must be lixiviated with warm water, and allowed to settle in a large cistern. The clear supernatant liquor, being drawn off, must be evaporated, and then crystallised. A second crystallisation finishes the process, and furnishes a marketable alum. Thus the Roman alum is made, which is covered with a fine red film of peroxide of iron.

2.Alum Manufacture from Alum Schist.—The greater portion of the alum found in British commerce is made from alum-slate and analogous minerals. This slate contains more or less iron pyrites, mixed with coaly or bituminous matter, which is occasionally so abundant as to render them somewhat combustible. In the strata of brown coal and bituminous wood, where the upper layers lie immediately under clay beds, they consist of the coaly substance rendered impure with clay and pyrites. This triple mixture constitutes the essence of all good alum schists, and it operates spontaneously towards the production of sulphate of alumina. The coal serves to make the texture open, and to allow the air and moisture to penetrate freely, and to change the sulphur and iron present into acid and oxide. When these schists are exposed to a high temperature in contact with air, the pyrites loses one half of its sulphur, in the form of sublimed sulphur or sulphurous acid, and becomes a black sulphuret of iron, which speedily attracts oxygen, and changes to sulphate of iron, or green vitriol. The brown coal schists contain, commonly, some green vitriol crystals spontaneously formed in them. The sulphate of iron transfers its acid to the clay, progressively, as the iron, by the action of the air with a little elevation of temperature, becomes peroxidised; whereby sulphate of alumina is produced. A portion of the green vitriol remains, however, undecomposed, and so much the more as there may happen to be less of other salifiable bases present in the clay slate. Should a little magnesia or lime be present, the vitriol gets more completely decomposed, and a portion of Epsom salt and gypsum is produced.

The manufacture of alum from alum schists may be distributed under the six following heads:—1. The preparation of the alum slate. 2. The lixiviation of the slate. 3. The evaporation of the lixivium. 4. The addition of the saline ingredients, or the precipitation of the alum. 5. The washing of the aluminous salts; and 6. The crystallisation.

1.Preparation of the Alum Slate.—Some alum slates are of such a nature that, being piled in heaps in the open air, and moistened from time to time, they get spontaneously hot, and by degrees fall into a pulverulent mass, ready to be lixiviated. The greater part, however, require the process of ustulation, from which they derive many advantages. The cohesion of the dense slates is thereby so much impaired that their decomposition becomes more rapid; the decomposition of the pyrites is quickened by the expulsion of a portion of the sulphur; and the ready-formed green vitriol is partly decomposed by the heat, with a transference of its sulphuric acid to the clay, and the production of sulphate of alumina.

Such alum-slates as contain too little bitumen or coal for the roasting process must be interstratified with layers of small coal or brushwood over an extensive surface. AtWhitby the alum rock, broken into small pieces, is laid upon a horizontal bed of fuel, composed of brushwood; but at Hurlett small coal is chiefly used for the lower bed. When about four feet of the rock is piled on, fire is set to the bottom in various parts; and whenever the mass is fairly kindled, more rock is placed over the top. At Whitby this piling process is continued till the calcining heap is raised to the height of 90 or 100 feet. The horizontal area is also augmented at the same time till it forms a great bed nearly 200 feet square, having therefore about 100,000 yards of solid measurement. The rapidity of the combustion is tempered by plastering up the crevices with small schist moistened. When such an immense mass is inflamed, the heat is sure to rise too high, and an immense waste of sulphur and sulphuric acid must ensue. This evil has been noticed at the Whitby works. At Hurlett the height to which the heap is piled is only a few feet, while the horizontal area is expanded; which is a much more judicious arrangement. At Whitby 130 tons of calcined schist produce on an average 1 ton of alum. In this humid climate it would be advisable to pile up on the top of the horizontal strata of brushwood or coal, and schist, a pyramidal mass of schist, which having its surface plastered smooth, with only a few air-holes, will protect the mass from the rains, and at the same time prevent the combustion from becoming too vehement. Should heavy rains supervene, a gutter must be scooped out round the pile for receiving the aluminous lixivium, and conducting it into the reservoir.

It may be observed, that certain alum schists contain abundance of combustible matter, to keep up a suitable calcining heat after the fire is once kindled; and therefore nothing is needed but the first layer of brushwood, which, in this case, may be laid over the first bed of the bituminous schist.

A continual, but very slow, heat, with a smothered fire, is most beneficial for the ustulation of alum slate. When the fire is too brisk, the sulphuret of iron may run with the earthy matters into a species of slag, or the sulphur will be dissipated in vapour, by both of which accidents the product of alum will be impaired. Those bituminous alum schists which have been used as fuel under steam boilers have suffered such a violent combustion that their ashes yield almost no alum. Even the best regulated calcining piles are apt to burn too briskly in high winds, and should have their draught-holes carefully stopped under such circumstances. It may be laid down as a general rule, that the slower the combustion the richer the roasted ore will be in sulphate of alumina. When the calcination is complete, the heap diminishes to one half its original bulk; it is covered with a light reddish ash, and is open and porous in the interior, so that the air can circulate freely throughout the mass. To favour this access of air, the masses should not be too lofty; and in dry weather a little water should be occasionally sprinkled on them, which, by dissolving away some of the saline matter, will make the interior more open to the atmosphere.

When the calcined mineral becomes thoroughly cold, we may proceed to the lixiviation. But as, from the first construction of the piles or beds till their complete calcination, many weeks, or even months, may elapse, care ought to be taken to provide a sufficient number or extent of them, so as to have an adequate supply of material for carrying on the lixiviating and crystallising processes during the course of the year, or at least during the severity of the winter season, when the calcination may be suspended, and the lixiviation becomes unsatisfactory. The beds are known to be sufficiently decomposed by the efflorescence of the salt which appears upon the stones, from the strong aluminous taste of the ashes, and from the appropriate chemical test of lixiviating an aliquot average portion of the mass, and seeing how much alum it will yield to solution of muriate or sulphate of potash.

2.The Lixiviation.—The lixiviation is best performed in stone-built cisterns; those of wood, however strong at first, are soon decomposed, and need repairs. They ought to be erected in the neighbourhood of the calcining heaps, to save the labour of transport, and so arranged that the solutions from the higher cisterns may spontaneously flow into the lower. In this point of view, a sloping terrace is the best situation for an alum work. In the lowest part of this terrace, and in the neighbourhood of the boiling-house, there ought to be two or more large deep tanks, for holding the crude lixivium, and they should be protected from the rain by a proper shed. Upon a somewhat higher level the cisterns of the clear lixivium may be placed. Into the highest range of cisterns the calcined mineral is to be put, taking care to lay the largest lumps at the bottom, and to cover them with lighter ashes. A sufficient quantity of water is now to be run over it, and allowed to rest for some time. The lixivium may then be drawn off, by a stopcock connected with a pipe at the bottom of the cistern, and run into another cistern at a somewhat lower level. Fresh water must now be poured on the partly exhausted schist, and allowed to remain for a sufficient time. This lixivium, being weak, should be run off into a separate tank. In some cases a third addition of fresh water may be requisite, and the weak lixivium which is drawn off may be reserved for a fresh portion of calcined mineral. In order to save evaporation, it is always requisite to strengthen weakleys by employing them instead of water for fresh portions of calcined schist. Upon the ingenious disposition and form of these lixiviating cisterns much of the economy and success of an alum work depend. The hydrometer should be always used to determine the degree of concentration which the solutions acquire.

The lixiviated stone being thus exhausted of its soluble ingredients, is to be removed from the cisterns, and piled up in a heap in any convenient place, where it may be left either spontaneously to decompose, or, after drying, may be subjected to another calcination.

The density of the solution may be brought, upon an average, up to the sp. gr. of from 1·09 to 1·15. The latter density may always be obtained by pumping up the weaker solutions upon fresh calcinedmine. This strong liquor is then drawn off, when the sulphate of lime, the oxide of iron, and the earths are deposited. It is of advantage to leave the liquor exposed for some time, whereby the green vitriol may pass into a persulphate of iron with the deposition of some oxide, while the liberated acid may combine with some of the clay present, so as to increase the quantity of sulphate of alumina. The manufacture of alum is the more imperfect, as the quantity of sulphate of iron left undecomposed is greater, and therefore every expedient ought to be tried to convert the sulphate of iron into sulphate of alumina.

3.The evaporation of the Schist Lixivium.—As the aluminous liquors, however well settled at first, are apt, on the great scale, to deposit earthy matters in the course of their concentration by heat, they are best evaporated by a surface fire, such as that employed at Hurlett and Campsie. A water-tight stone cistern must be built, having a layer of well rammed clay behind the flags or tiles which line its bottom and sides. This cistern may be 4 or 6 feet wide, 2 or 3 feet deep, and 30 or 40 feet long, and it is covered in by an arch of stone or brickwork. At one extremity of this tunnel, or covered canal, a fire-grate is set, and at the other a lofty chimney is erected. The cistern being filled to the brim with the alum ley, a strong fire is kindled in the reverberatory grate, and the flame and hot air are forced to sweep along the surface of the liquor, so as to keep it in constant ebullition, and to carry off the aqueous parts in vapour. The soot which is condensed in the process falls to the bottom, and leaves the body of the liquor clear. As the concentration goes on, more of the rough lixivium is run in from the settling cistern, placed on a somewhat higher level, till the whole gets charged with a clear liquor of a specific gravity sufficiently high for transferring into the proper lead boilers.

At Whitby, the lead pans are 10 feet long, 4 feet 9 inches wide, 2 feet 2 inches deep at the one end, and 2 feet 8 inches deep at the other. This increase of depth and corresponding slope, facilitates the decantation of the concentrated lixivium by means of a syphon, applied at the lower end. The bottom of the pan is supported by a series of parallel iron bars, placed very near each other. In these lead pans the liquor is concentrated, at a brisk boiling heat, by means of the flame of a flue beneath them. Every morning the pans are emptied into a settling cistern of stone or lead. The specific gravity of the liquor should be about 1·4 or 1·5, being a saturated solution of the saline matters present. The proper degree of density must vary, however, with different kinds of lixivia, and according to the different views of the manufacturer. For a liquor which consists of two parts of sulphate of alumina, and one part of sulphate of iron, a specific gravity of 1·25 may be sufficient; but for a solution which contains two parts of sulphate of iron to one of sulphate of alumina, so that the green vitriol must be withdrawn first of all by crystallisation, a specific gravity of 1·4 may be requisite.

The construction of an evaporating furnace well adapted to the concentration of aluminous and other crude lixivia, is described underSoda. The liquor basin may be made of tiles or flags puddled in clay, and secured at the seams with a goodhydrauliccement. A mortar made of quicklime mixed with the exhausted schist in powder, and iron turnings, is said to answer well for this purpose. Sometimes over the reverberatory furnace a flat pan is laid, instead of the arched top, into which the crude liquor is put for neutralisation and partial concentration. In Germany, such a pan is made of copper, because iron would waste too fast, and lead would be apt to melt. From this preparation basin the under evaporating trough is gradually supplied with hot liquor. At one side of this lower trough, there is sometimes a door, through which the sediment may be raked out as it accumulates upon the bottom. Such a contrivance is convenient for this mode of evaporation, and it permits, also, any repairs to be readily made; but, indeed, an apparatus of this kind, well mounted at first, will serve for many years.

In the course of the final concentration of the liquors, it is customary to add some of the mother waters of a former process, the quantity of which must be regulated by a proper analysis and knowledge of their contents. If these mother waters contain much free sulphuric acid, from the peroxidation of their sulphate of iron, they may prove useful in dissolving a portion of the alumina of the sediment which is always present in greater or less quantity.

4.The precipitation of the Alum by adding Alkaline Salts.—As a general rule, it is most advantageous to separate, first of all, from the concentrated clear liquors, the alum in the state of powder or small crystals, by addition of the proper alkaline matter, and to leave the mingled foreign salts, such as the sulphate of iron or magnesia, in solution, instead of trying to abstract these salts by a previous crystallisation. In this way we not only simplify and accelerate the manufacture of alum, and leave the mother waters to be worked up at any convenient season, but we also avoid the risk of withdrawing any of the sulphate of alumina with the sulphate of iron or magnesia. On this account, the concentration of the liquor ought not to be pushed so far as that, when it gets cold, it should throw out crystals, but merely to the verge of this point. This density may be determined by suitable experiments.

The clear liquor should now be run off into the precipitation cistern, and have the proper quantity of sulphate or muriate of potash, or impure sulphate or carbonate of ammonia added to it. The sulphate of potash, which is the best precipitant, forms 18·34 parts out of 100 of crystallised alum; and therefore that quantity of it, or its equivalent in muriate of potash, or other potash or ammoniacal salts, must be introduced into the aluminous liquor. Since sulphate of potash takes 10 parts of cold water to dissolve it, but is much more soluble in boiling water, and since the precipitation of alum is more abundant the more concentrated the mingled solutions are, it would be prudent to add the sulphate solution as hot as may be convenient; but, as muriate of potash is fully three times more soluble in cold water, it is to be preferred as a precipitant, when it can be procured at a cheap rate. It has, also, the advantage of decomposing the sulphate of iron present into a muriate, a salt very difficult of crystallisation, and, therefore, less apt to contaminate the crystals of alum. The quantity of alkaline salts requisite to precipitate the alum, in a granular powder, from the lixivium, depends on their richness in potash or ammonia, on the one hand, and on the richness of the liquors in sulphate of alumina on the other; and it must be ascertained, for each large quantity of product, by a preliminary experiment in a precipitation glass. Here, an aliquot measure of the aluminous liquor being taken, the liquid precipitant must be added in successive portions, as long as it causes any cloud, when the quantity added will be indicated by the graduation of the vessel. A very exact approximation is not practicable upon the great scale; but, as the mother waters are afterwards mixed together in one cistern, any excess of the precipitant, at one time, is corrected by excess of aluminous sulphate at another, and the resulting alum meal is collected at the bottom. When the precipitated saline powder is thoroughly settled and cooled, the supernatant mother water must be drawn off by a pump, or rather a syphon or stopcock, into a lower cistern. The more completely this drainage is effected, the more easily and completely will the alum be purified.

This mother liquor has, generally, a specific gravity of 1·4 at a medium temperature of the atmosphere, and consists of a saturated solution of sulphate or muriate of black and red oxide of iron, with sulphate of magnesia, in certain localities, and muriate of soda, when the soaper’s salt has been used as a precipitant, as also a saturated solution of sulphate of alumina. By adding some of it, from time to time, to the fresh lixivia, a portion of that sulphate is converted into alum; but, eventually, the mother water must be evaporated, so as to obtain from it a crop of ferruginous crystals; after which it becomes capable, once more, of giving up its alum to the alkaline precipitants.

When the aluminous lixivia contain a great deal of sulphate of iron, it may be good policy to withdraw a portion of it by crystallisation before precipitating the alum. With this view, the liquors must be evaporated to the density of 1·4, and then run off into crystallising stone cisterns. After the green vitriol has concreted, the liquor should be pumped back into the evaporating pan, and again brought to the density of 1·4. On adding to it, now, the alkaline precipitants, the alum will fall down from this concentrated solution, in a very minute crystalline powder, very easy to wash and purify. But this method requires more vessels and manipulation than the preceding, and should only be had recourse to from necessity; since it compels us to carry on the manufacture of both the valuable alum and the lower priced salts at the same time; moreover, the copperas extracted at first from the schist liquors carries with it, as we have said, a portion of the sulphate of alumina, and acquires thereby a dull aspect; whereas the copperas obtained after the separation of the alum is of a brilliant appearance.

5.The washing, or edulcoration, of the Alum Powder.—This crystalline pulverulent matter has a brownish colour, from the admixture of the ferruginous liquors; but it may be freed from it by washing with very cold water, which dissolves not more than one sixteenth of its weight of alum. After stirring the powder and the water well together, the former must be allowed to settle, and then the washing must be drawn off. A second washing will render the alum nearly pure. The less water is employed, and the more effectually it is drained off, the more complete is the process. The second water may be used in the first washing of another portion ofalum powder, in the place of pure water. These washings may be added to the schist lixivia.

6.The crystallisation.—The washed alum is put into a lead pan, with just enough water to dissolve it at a boiling heat; fire is applied, and the solution is promoted by stirring. Whenever it is dissolved in a saturated state, it is run off into the crystallising vessels, which are calledrochingcasks. These casks are about five feet high, three feet wide in the middle, somewhat narrower at the ends; they are made of very strong staves, nicely fitted to each other, and held together by strong iron hoops, which are driven onpro tempore, so that they may be easily knocked off again, in order to take the staves asunder. The concentrated solution, during its slow cooling in these close vessels, forms large regular crystals, which hang down from the top, and project from the sides, while a thick layer or cake lines the whole interior of the cask. At the end of eight or ten days, more or less, according to the weather, the hoops and staves are removed, when a cask of apparently solid alum is disclosed to view. The workman now pierces this mass with a pickaxe at the side near the bottom, and allows the mother water of the interior to run off on the sloping stone floor into a proper cistern, whence it is taken and added to another quantity of washed powder to be crystallised with it. The alum is next broken into lumps, exposed in a proper place to dry, and is then put into the finished bing for the market. There is sometimes a little insoluble basic alum (subsulphate) left at the bottom of the cask. This being mixed with the former mother liquors, gets sulphuric acid from them; or, being mixed with a little sulphuric acid, it is equally converted into alum.

When, instead of potash or its salts, the ammoniacal salts are used, or putrid urine, with the aluminous lixivia, ammoniacal alum is produced, which is perfectly similar to the potash alum in its appearance and properties. At a gentle heat both lose their water of crystallisation, amounting to 451⁄2per cent. for the potash alum, and 48 for the ammoniacal. The quantity of acid is the same in both, as, also, very nearly the quantity of alumina, as the following analyses will show:

When heated pretty strongly, the ammoniacal alum loses its sulphuric acid and ammonia, and only the earth remains. This is a very convenient process for procuring pure alumina. Ammoniacal alum is easily distinguished from the other by the smell of ammonia which it exhales when triturated with quicklime. The Roman alum, made from alum stone, possesses most of the properties of the schist-made alums, but it has a few peculiar characters: it crystallises always in opaque cubes, whereas the common alum crystallises in transparent octahedrons. It is probable that Roman alum is a sulphate of alumina and potash, with a slight excess of the earthy ingredient. It is permanent when dissolved in cold water; for after a slow evaporation it is recovered in a cubical form. But when it is dissolved in water heated to 110° Fahr. and upwards, or when its solution is heated above this pitch, subsulphate of alumina falls, and on evaporation octahedral crystals of common alum are obtained. The exact composition of the Roman alum has not been determined, as far as I know. It probably differs from the other also in its water of crystallisation. The Roman alum contains, according to MM. Thenard and Roard, only1⁄2200of sulphate of iron, while the common commercialalums contain1⁄1000. It may be easily purified by solution, granulation, crystallisation, and washing, as has been already explained.

Alum is made extensively in France from an artificial sulphate of alumina. For this purpose clays are chosen as free as possible from carbonate of lime and oxide of iron. They are calcined in a reverberatory furnace, in order to expel the water, to peroxidise the iron, and to render the alumina more easily acted on by the acid. The expulsion of the water renders the clay porous and capable of absorbing the sulphuric acid by capillary attraction. The peroxidation of the iron renders it less soluble in the sulphuric acid; and the silica of the clay, by reacting on the alumina, impairs its aggregation, and makes it more readily attracted by the acid. The clay should, therefore, be moderately calcined; but not so as to indurate it like pottery ware, for it would then suffer a species of siliceous combination which would make it resist the action of acids. The clay is usually calcined in a reverberatory furnace, the flame of which serves thereafter to heat two evaporating pans and a basin for containing a mixture of the calcined clay and sulphuric acid. As soon as the clay has become friable in the furnace it is taken out, reduced to powder, and passed through a fine sieve. With 100 parts of the pulverised clay, 45 parts of sulphuric acid, of sp. gr. 1·45, are well mixed, in a stone basin, arched over with brickwork. The flame and hot air of a reverberatory furnace are made to play along the mixture, in the same way as described for evaporating the schist liquors. SeeSoda. The mixture, being stirred from time to time, is, at the end of a few days, to be raked out, and to be set aside in a warm place, for the acid to work on the clay, during six or eight weeks. At the end of this time it must be washed, to extract the sulphate of alumina. With this view, it may be treated like the roasted alum ores above described. If potash alum is to be formed, this sulphate of alumina is evaporated to the specific gravity of 1·38; but if ammonia alum, to the specific gravity of only 1·24; because the sulphate of ammonia, being soluble in twice its weight of water, will cause a precipitation of pulverulent alum from a weaker solution of sulphate of alumina than the less soluble sulphate of potash could do.

The alum stone, from which the Roman alum is made, contains potash. The following analysis ofalunite, by M. Cordier, places this fact in a clear light:—

To transform this compound into alum, it is merely necessary to abstract the hydrate of alumina. The ordinary alum stone, however, is rarely so pure as the above analysis would seem to show; for it contains a mixture of other substances; and the above are in different proportions.

Alum is very extensively employed in the arts, most particularly in dyeing, lake making, dressing sheep-skins, pasting paper, in clarifying liquors, &c. Its purity for the dyer may be tested by prussiate of potash, which will give solution of alum a blue tint in a few minutes if it contain even a very minute portion of iron. A bit of nut-gall is also a good test of iron.

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