Chapter VII: Part III (2)

(_a._) _Iron._--It occurs in great abundance in nature. It is found in several places in America in the metallic state, and it likewise occurs in the same state in meteors. It occurs chiefly as the oxide (red hematite, brown hematite, magnetic oxide, etc.), and frequently in combination with sulphur. Iron also forms a constituent of the blood.

Metallic iron is of a grey color, and presents the metallic lustre vividly when polished. It is very ductile, malleable, and tenacious. It is very hard at common temperatures, but soft and yielding at a red heat.

In dry and cold air, iron does not oxidize, but when the air is dry and moist, it oxidizes rapidly. This likewise takes place with great rapidity when the metal is heated to redness. When submitted to a white heat iron burns with brilliant scintillations.

_Protoxide of Iron_ (FeO).--This oxide does not occur pure in nature, but in union with the peroxide of iron and other substances. It presents the form of a black powder, and has some metallic lustre, is brittle, and fuses at a high temperature to a vitreous looking mass. It is attracted by the magnet, and of course is susceptible of becoming magnetic itself. It forms with water a hydrate, but this passes so rapidly into a state of higher oxidation, that it is difficult to keep it in the pure state.

_Magnetic Oxide of Iron_ (FeO + Fe^{2}O^{3}).--This peculiar oxide is of a dark color, and is magnetic, so that tacks or small nails adhere to it when brought in contact with it. It is the variety of the oxide termed "loadstone." It is found frequently crystallized in octahedrons in Scandinavia and other places. Magnetic oxide of iron is produced when red-hot iron is hammered.

_Sesquioxide of Iron_ (Fe^{2}O^{3}).--This oxide is found native in great abundance as red hematite and specular iron, crystallized in the rhombic form. In the crystalline state it is of a blackish-grey color, and possessed of the metallic lustre. When powdered, it forms a brownish-red mass. When artificially prepared, it presents the appearance of a blood-red powder. It is not magnetic, and has less affinity for acids than the protoxide. Its hydrate is found native as brown hematite.

By exposing the peroxide of iron to the oxidation flame, it is not acted upon, but in the reduction flame it becomes reduced to the magnetic oxide.

The oxides of iron are dissolved by borax in the oxidation flame to a clear dark-yellow or dark-red bead, which appears lighter while cooling, and yellowish when cold. In the presence of a very small quantity of iron, the bead appears colorless when cold. If the iron is increased, the bead is opaque while cooling, and of a dirty dark-yellow color when cold. In the reduction flame, and fused upon platinum wire, the bead appears dark green (FeO + Fe^{2}O^{3}). By the addition of some tin, and fused upon charcoal, the bead appears bluish-green, or not unlike that of sulphate of iron.

Microcosmic salt dissolves the oxides of iron in the oxidation flame to a clear bead, which, by the addition of a considerable quantity of iron, becomes of an orange color while hot, but gets lighter while cooling, presenting finally a greenish hue, and gradually becoming lighter, till, when cold, it is colorless. If the iron is increased, the hot bead presents a dark red color, but while cooling a brownish-red, which changes to a dirty-green, and, when cold, to a brownish-red color. The decrease of the color during the transition from the hot to the cold state is still greater in the bead formed by the microcosmic salt.

In the reduction flame no change is visible if the quantity of iron be small. By the addition of more iron, the hot bead appears red, and while cooling, changes to yellow, then green, and, when cold, is of a dull red. By fusing the bead on charcoal with a small addition of tin, it exhibits, while cooling, a bluish-green color, but, when cold, is colorless.

The oxides of iron are not dissolved in the oxidation flame by fusion with carbonate of soda. By ignition with soda upon charcoal in the reduction flame, they are absorbed and reduced to the metallic state. Cut out this portion of the charcoal; grind it with the addition of some water in an agate mortar, for the purpose of washing off the carbon particles, when the iron will remain as a grey magnetic powder.

(_b._) _Cobalt_ (Co) occurs in combination with arsenic and sulphur, and associated with nickel and iron. It is found occasionally in combination with selenium, and there are a traces of it in meteoric iron. In the metallic state it is of a light, reddish-grey color, rather brittle, and only fusible at a strong white heat; at common temperatures it is unalterable by air or water. At a red heat, it oxidizes slowly and decomposes water; at a white heat it burns with a red flame. Cobalt is soluble in dilute sulphuric or hydrochloric acid by the aid of heat, whereby hydrogen is eliminated. These solutions have a fine red color.

_Protoxide of Cobalt_ (CoO).--It is an olive-green powder, but, by exposure to the air, it becomes gradually brown. Its hydrate is a rich red powder. The solution of its salts is red, but the aqueous solution is often blue.

When heated in the oxidation flame, the protoxide is converted into the black proto-sesquioxide (CoO + Co^{2}O^{3}). In the reduction flame it shrinks and is reduced without fusion to the metallic state. It is now attracted by the magnet and acquires lustre by compression.

Borax dissolves it in the oxidation flame, and produces a clear, intensely colored blue bead, which remains transparent and of the same beautiful blue when cold. This blue is likewise manifest even if the bead be heated intermittingly. If the cobalt exists in considerable quantity, the color of the bead is so intense as to appear almost black.

This reaction of cobalt is so characteristic and sensitive that it can detect a minute trace.

With microcosmic salt the same reaction is exhibited, but not so sensitive, nor is the bead so intensely colored when cold as that with borax.

By fusion with carbonate of soda upon a platinum wire, with a very small portion of cobalt, a bright red colored mass is produced which appears grey, or slightly green when cold. By fusion upon platinum foil the fused portion floats down from the sides, and the foil is coated around the undissolved part, with a thin, dark-red sublimate. When fused upon charcoal, and in the reduction flame, it is reduced with soda to a grey powder, which is attracted by the magnet, and exhibits the metallic lustre by compression.

_Sesquioxide of Cobalt_ (Co^{2}O^{3}).--It is a dark brown powder. Its hydrate (2HO + Co^{2}O^{3}) is a brown powder. It is soluble only in acetic acid as the acetate of the sesquioxide. All other acids dissolve its salts to protoxide, the hydrochloric acid producing chloric gas. By ignition in the oxidation flame, it is converted into the proto-sesquioxide (CoO + Co^{2}O^{3}) and produces with reagents before the blowpipe the same reactions as the protoxide.

(_c._) _Nickel_ (Ni).--This metal occurs invariably associated with cobalt, and in analogous combinations, chiefly as the arsenical nickel. In the metallic state it is greyish, silver-white, has a high lustre, is hard, and malleable both cold and hot. At common temperatures, it is unalterable either in dry or moist air. When ignited, it tarnishes. It is easily dissolved by nitric acid, but very slowly by dilute sulphuric or hydrochloric acid, producing hydrogen.

_Protoxide of Nickel _(NiO).--It is in the form of small greyish-black octahedrons, or a dark, greenish-grey powder. Its hydrate is a green powder. Both are unalterable in the air, and are soluble in nitric, sulphuric, and hydrochloric acids, to a green liquid. The protoxide is the base of the salts of nickel, which in the anhydrous state are yellow, and when hydrated are green. The soluble neutral salts change blue litmus paper to red. By ignition in the oxidation flame, protoxide of nickel is unaltered. In the reduction flame and upon charcoal, it becomes reduced, and forms a grey adherent powder, which is infusible, and presents the metallic lustre by compression, and is magnetic. Borax dissolves it in the oxidation flame very readily to a clear bead, of a reddish-violet or dark yellow color, but yellow or light red when cold. If there is but a small quantity of the oxide present, it is colorless. If more of the oxide be present, the bead is opaque and dark brown, and appears, while cooling, transparent and dark red. By the addition of a salt of potassa (the nitrate or carbonate) a blue or a dark purple colored bead is produced. The borax bead, in the reduction flame, is grey, turbid, or completely opaque from the reduced metallic particles. After a continued blast, the bead becomes colorless, although the particles are not fused. If the nickel contains cobalt, it will now be visible with its peculiar blue color. Upon charcoal, and by the addition of some tin, the reduction of the oxide of nickel is easily effected, while the reduced nickel fuses with the tin.

The oxide of nickel is dissolved by microcosmic salt in the oxidation flame to a clear bead, which appears reddish while hot, but yellow and sometimes colorless when cooling. If a considerable quantity of nickel be present the heated bead is of a brown color, but orange when cooled. In the reduction flame, and upon platinum wire, the color of the bead is orange when cold; but upon charcoal, and with the addition of a little tin, the bead appears grey and opaque. After being submitted to the blowpipe flame all the nickel is reduced, and the bead becomes colorless.

Carbonate of soda does not affect it in the oxidation flame, but in the reduction flame and upon charcoal, it is absorbed and reduced, and remains, after washing off the carbon, as a white metallic powder, which is infusible, and has a greater attraction for the magnet than iron.

_Sesquioxide of Nickel_ (Ni^{2}O^{3}).--It is in the form of a black powder, and does not combine with other substances, unless it is reduced to the protoxide. It exhibits before the blowpipe the same behavior as the protoxide.

GROUP SIXTH.--ZINC, CADMIUM, ANTIMONY, TELLURIUM.

The substances of this group can be reduced upon charcoal by fusion with carbonate of soda, but the reduced metals are volatilized, and cover the charcoal with sublimates.

(_a._) _Zinc_ (Zn).--This metal is found in considerable abundance, but never occurs in the pure metallic state, but in combination with other substances, chiefly as sulphide in zinc blende, as carbonate in calamine, and as the silicate in the kieselzinc ore; also, with sulphuric acid, the "vitriol of zinc."

Zinc is of a bluish-white color and metallic lustre, is crystalline and brittle when heated 400 deg.F., but malleable and ductile between 200 deg. and 300 deg.. It will not oxidize in dry air, but tarnishes if exposed to air containing moisture, first becomes grey, and then passes into the white carbonate. It decomposes in water at a glowing heat. It is dissolved by diluted acids, while hydrogen is eliminated. It melts at about 775 deg., and distills when exposed to a white heat in a close vessel. When heated over 1000 deg. in the open air, it takes fire, and burns with a bluish-white light, and with a thick white smoke of oxide of zinc.

_Oxide of Zinc_ (ZnO).--In the pure state, oxide of zinc is a white powder, infusible, and not volatile. It is readily soluble in acids after being heated strongly. Its soluble neutral salts, when dissolved in water, change blue litmus paper to red. Its salts, with organic acids, are decomposed by ignition, and the carbonate of zinc remains.

The oxide of zinc turns yellow by being ignited in the oxidation flame, but it is only visible by daylight; this color changes to white when cold. It does not melt, but produces a strong light, and it is not volatile.

It disappears gradually in the flame of reduction, while a white smoke sublimates upon the charcoal. This sublimate is yellow while hot, but changes to white when cold. The cause of this is, that the oxide is reduced, is volatilized, and re-oxidized, by going through the external flame in the form of a metallic vapor.

Borax dissolves oxide of zinc in the flame of oxidation easily to a clear bead, which is yellow while hot, and colorless when cold. The bead becomes, by the addition of more oxide, enamelled, while cooling. If the bead is heated with the intermittent flame, it is milk-white when cold. When heated in the flame of reduction upon platinum wire, the bead at first appears opaque, and of a greyish color, but becomes clear again after a continued blast.

When heated upon charcoal in the reduction flame, it is reduced to a metal; but, at the same moment, is volatilized, and sublimes as oxide of zinc upon the charcoal, about one line's distance from the assay. This is likewise the case with the microcosmic salt, except that it is more easily volatilized in the reduction flame.

Carbonate of soda does not dissolve the oxide of zinc in the flame of oxidation. In the reduction flame and upon charcoal, the oxide of zinc is reduced to the metallic state, and is volatilized with a white vapor of the zinc oxide, which sublimes on the charcoal and exhibits a yellow color while hot, and which changes to white when cold. By a strong heat the reduced zinc burns with a white flame.

Moistened with a solution of cobalt oxide, and heated strongly in the flame of oxidation, zinc oxide becomes of a yellowish-green color while hot, and changes to a beautiful green color when cold.

(_b._) _Cadmium_ (Cd).--This is one of the rare metals. It occurs in combination with sulphur in _greenockite_, and in some ores of zinc. It was detected first in the year 1818, and presents itself as a tin-white metal of great lustre, and susceptible of a fine polish. It has a fibrous structure, crystallizes easily in regular octahedrons, presenting often the peculiar arborescent appearance of the fern. It is soft, but harder and more tenacious than tin; it can be bent, filed, and easily cut: it imparts to paper a color like that of lead. It is very malleable and ductile, and can be hammered into thin leaves. It is easily fused, and melts before it glows (450 deg.). At a temperature not much over the boiling point of mercury, it begins to boil, and distills, the vapor of the metal possessing no peculiar odor. It is unalterable in the air for a long time, but at length it tarnishes and presents a greyish-white, half metallic color. This metal easily takes fire when heated in the air, and burns with a brownish-yellow vapor, while it deposits a yellow sublimate upon surrounding bodies. It is easily soluble in acids with the escape of hydrogen, the solutions being colorless. Its salts, soluble in water, are decomposed by ignition in free air. Its soluble neutral salts change blue litmus paper to red. The salts, insoluble in water, are readily dissolved in acids.

_Oxide of Cadmium_ (CdO).--This oxide is of a dark orange color. It does not melt, and is not volatile, not even at a very high temperature. Its hydrate is white, loses in the heat its hydratic water, and absorbs carbonic acid from the air when it is kept in open vessels.

Cadmium oxide is unaltered when exposed upon platinum wire in the flame of oxidation. When heated upon charcoal in the flame of reduction it disappears in a very short time, while the charcoal is coated with a dark orange or yellow powder, the color of which is more visible after it is cooled. The portions of this sublimate furthest from the assay present a visible iridescent appearance. This reaction of cadmium is so characteristic and sensitive that minerals (for instance, calamine, carbonate of zinc) which contains from one to five per cent. of carbonate of cadmium, will give a dark yellowish ring of cadmium oxide, a little distance from the assay, after being exposed for a few moments to the flame of reduction. This sublimate is more visible when cold, and is produced some time previous to the reduction of the zinc oxide. If a vapor of the latter should appear, it indicates that it has been exposed too great a length of time to the flame.

Borax dissolves a considerable quantity of cadmium oxide upon a platinum wire to a clear yellow bead, which, when cold, is almost colorless. If the bead is nearly saturated with the cadmium oxide, it appears milk-white when intermittingly heated. If the bead is completely saturated, it retains its opalescent appearance. Upon charcoal, and in the flame of reduction, the bead intumesces, the cadmium oxide becomes reduced to metal; this becomes volatilized and re-oxidized, and sublimes upon the charcoal as the yellow cadmium oxide.

In the oxidation flame, microcosmic salt dissolves a large quantity of it to a clear bead, which, when highly saturated and while hot, is yellowish colored, but colorless when cold. By complete saturation, the bead is enamel-white when cold.

Upon charcoal, in the flame of reduction, the bead is slowly and only partially reduced, a scanty sublimate being produced on the charcoal. The addition of tin promotes the reduction.

Carbonate of soda does not dissolve cadmium oxide in the oxidation flame. In the reduction flame, upon charcoal, it is reduced to metal, and is volatilized to a red-brown or dark, red sublimate of cadmium oxide upon the charcoal, at a little distance from the assay the charcoal presenting the characteristic iridescent appearance. This reaction is still more sensitive if the cadmium oxide is heated _per se_ in the reduction flame.

_Antimony_ (Sb).--This metal is found in almost every country. It principally occurs as the tersulphide (SbS^{3}), either pure or combined with other sulphides, particularly with basic sulphides. Sometimes it occurs as the pure metal, and rarer in a state of oxidation as an antimonious acid and as the oxysulphide.

In the pure state, antimony has a silver-white color, with much lustre, and presents a crystalline structure. The commercial and impure metal is of a tin-white color, and may frequently be split in parallel strata. It is brittle and easily pulverized. It melts at a low red heat (810 deg.), is volatilized at a white heat, and can be distilled. At common temperatures it is not affected by the air. At a glowing heat it takes fire, and burns with a white flame, and with white fumes, forming volatile antimonious acid. Common acids oxidize antimony, but dissolve it slightly. It is soluble in aqua regia (nitro-hydrochloric acid).

_Sesquioxide of Antimony_ (Sb^{2}O^{3}).--In the pure state this oxide is a white powder, is fusible at a dull red heat to a yellow liquid, which, after cooling, is greyish-white and crystalline. If it is heated excluded from the air, it can be volatilized completely; it sublimes in bright crystals having the form of needles. It occurs sometimes in nature as white and very bright crystals. It takes fire when heated in the open air, and burns with a white vapor to antimonious acid. It fuses with the ter-sulphide of antimony to a red bead. It is distinguished from the other oxides of antimony by the readiness with which it is reduced to the metallic state upon charcoal, and by its easy fusibility and volatility.

The sesquioxide is the base of some salts--for instance, the tartar emetic. It is not soluble in nitric acid, but is soluble in hydrochloric acid. This solution becomes milky by the addition of water. A part of the salts of the sesquioxide of antimony are decomposed by ignition. The haloid salts are easily volatilized, without decomposition. Its soluble neutral salts change blue litmus paper to red, and are converted, by admixture of water, into insoluble basic and soluble acid salts.

Antimonious acid (antimoniate of sesquioxide of antimony, Sb^{2}O^{3} + Sb^{2}O^{5}) is of a white color, but, when heated, of a light yellow color, but changes to white again when cold. It is infusible and unaltered by heat. It forms a white hydrate, and both are insoluble in water and nitric acid. It is partly soluble in hydrochloric acid, with the application of heat. The addition of water causes a precipitate in this solution.

_Antimonic Acid _(Sb^{2}O^{5}).--In the pure state this acid is a light yellow-colored powder. Its hydrate is white, and is insoluble in water and nitric acid. It is sparingly soluble in hot concentrated hydrochloric acid. It forms salts with every base, some of which are insoluble, and others sparingly so. Notwithstanding that antimonic acid is insoluble in water, it expels the carbonic acid from the solutions of the carbonates of the alkalies. Antimonic acid and its hydrate changes moistened blue litmus paper to red.

_Behavior of Antimony and its Oxides before the Blowpipe._

_Metallic Antimony_ fuses easily upon charcoal. When heated to glowing, and then removed from the flame, it continues to glow for awhile, and produces a thick white smoke. The vapor crystallizes gradually, and coats the assay with small crystals which iridesce like mother of pearl (sesquioxide of antimony). It is not volatile at the temperature of melted glass. Ignited in an open glass tube, it burns slowly with a white vapor, which condenses upon the cool part of the tube, and exhibits some indications of crystallization. This vapor consists of the sesquioxide, and can be driven by heat from one place to another, without leaving a residue. If the metallic antimony contains sulphide of antimony, there is a corresponding portion of antimonious acid produced, which remains as a white sublimate after the sesquioxide is removed.

_Sesquioxide of antimony_ melts easily, and sublimes as a white vapor. It may be prepared by precipitating and drying. When heated, it takes fire previous to melting, glows like tinder, and is converted into antimonious acid, which is now infusible. When heated upon charcoal in the flame of reduction, it is reduced to the metallic state, and partly volatilized. A white vapor sublimates upon the charcoal, while the external flame exhibits a greenish-blue color. Antimonious acid is infusible, produces a strong light, and is diminished in volume when heated in the external flame, during which time a dense white vapor sublimes upon the charcoal. It is not, however, in this manner reduced to the metallic state like the sesquioxide.

_Antimonic acid_, when first heated, becomes white, and is converted into antimonious acid. Hydrated antimonic acid, which is originally white, appears at first yellow while giving off water, and then becomes white again, while oxygen is expelled, and it is converted into antimonious acid.

The oxides of antimony produce, with blowpipe reagents, the following reactions: borax dissolves oxides of antimony in the oxidation flame in considerable quantity to a clear bead, which is yellow while hot, but colorless when cold. If the bead is saturated, a part of the oxide is volatilized as a white vapor. Upon charcoal, in the oxidation flame, it is completely volatilized, and the charcoal is covered with a white sublimate. Heated upon charcoal in the reducing flame, the bead is of a greyish color, and partially, if not wholly opaque, from the presence of reduced metallic particles. A continued heat will volatilize them, and the bead becomes clear. The addition of tin promotes the reduction.

Microcosmic salt dissolves the compounds of antimony in the flame of oxidation with intumescence, to a clear light-yellow colored bead, which when cold is colorless. Heated upon charcoal in the reduction flame, the bead is first turbid, but soon becomes transparent. The addition of tin renders the bead greyish while cooling, but a continued blast renders it transparent. Soda dissolves the compounds of antimony upon platinum wire in the oxidation flame, to a clear colorless bead, which is white when cold.

Upon charcoal, both in the oxidation and reduction flames, the antimony compounds are readily reduced to the metal, which is immediately volatilized, and produces a white incrustation of oxide of antimony upon the charcoal. If the antimony compounds are heated upon charcoal in the flame of reduction, with a mixture of carbonate of soda and cyanide of potassium (KCy), there are produced small globules of metallic antimony. At the same time, a part of the reduced metal is volatilized (this continues after the assay is removed from the flame) and re-oxidized. A white incrustation appears upon the charcoal, and the metallic globules are covered with small white crystals. If this white sublimate upon the charcoal is moistened with a solution of cobalt-oxide, and exposed to the reduction flame, a part of it is volatilized, while the other part passes into higher oxidation, and remains, after cooling, of a dirty dark-green color.

(_d._) _Tellurium_ (Te).--This is one of the rare metals. It occurs very seldom in the metallic state, but often with bismuth, lead, silver, and gold. Tellurium, in the pure state, is silver-white, very bright, of a foliated or lamellar structure, brittle, and easily triturated. It is inclined to crystallize. It is soluble in concentrated sulphuric acid without oxidation. The solution is of a fine purple color, and gives a precipitate with the addition of water.

_Tellurium in the Metallic form._--By the aid of heat it is oxidized in sulphuric acid, a portion of the oxygen of the acid oxidizing the metal, while sulphurous acid gas escapes. This solution is colorless, and is tellurous acid, dissolved in sulphuric acid. It melts at a low red heat, and volatilizes at a higher temperature. If tellurium is heated with free access of air, it takes fire, and burns with a blue color, the flame being greenish at the edges, while a thick white vapor escapes, which has a feeble acidulous odor.

_Tellurous Acid_ (TeO^{2}) is of a fine, granulous, crystalline or white earthy mass, which is partly soluble in water. The solution has a strong metallic taste, and an acid reaction upon litmus paper. Heated in a tube closed at one end until it begins to glow, it fuses to a yellow liquid which is colorless, crystalline, and opaque when cold. Beads of it remain usually transparent like glass. Heated upon platinum wire in the flame of oxidation, it melts, and is volatilized as a white vapor. When heated upon charcoal in the oxidation flame, it melts, and is reduced to the metallic state, but volatilizes and a sublimate of white tellurous acid is formed upon the charcoal. The edge of this deposit is usually red or dark-yellow.

Heated upon charcoal in the flame of reduction, it is rapidly reduced, the external flame exhibiting a bluish-green color.

Borax dissolves it in the oxidation flame upon platinum wire to a clear colorless bead which turns grey when heated upon charcoal, through the presence of reduced metallic particles. Upon charcoal, in the reduction flame, the bead is grey, caused by the reduced metal. After a continued blast, tellurium is completely volatilized, and the bead appears clear again, while a white sublimate is deposited upon the charcoal.

With microcosmic salt, the same reactions are produced.

With carbonate of soda, tellurous acid fuses upon platinum wire to a clear colorless bead, which is white when cold. Upon charcoal it is reduced, and forms _tellur-sodium_, which is absorbed by the charcoal, and metallic tellurium, which is volatilized, and deposits upon the charcoal a white incrustation (tellurous acid).

If tellurous acid, finely powdered charcoal, and carbonate of soda are mixed together, and the mixture be well ignited in a closed tube, until fusion is effected, and a few drops of boiled water are brought into the tube, they are colored purple, indicating the presence of _tellur-sodium._

_Telluric Acid _(TeO^{3}) forms six-sided prismatic crystals. It has not an acid, but rather a metallic taste. It changes blue litmus paper to red; is slowly soluble in water, and rather sparingly. Exposed to a high temperature, but not until glowing, the crystalline acid loses its water, and acquires an orange color, but still it preserves its crystalline form, although no longer soluble in water, and is in fact so much changed in its properties as to present the instance of an isomeric modification.

If telluric acid is heated gently in a closed tube, it loses water and turns yellow. Heated still more strongly, it becomes milk-white, oxygen is expelled, and it is converted into tellurous acid. The presence of oxygen can be recognized by the more lively combustion which an ignited splinter of wood undergoes when held in it. Telluric acid produces the same reactions with the blowpipe reagents as tellurous acid.

SEVENTH GROUP.--LEAD, BISMUTH, TIN.

The oxides of these metals are also reduced to the metallic state by fusion with soda upon charcoal in the flame of reduction, but they are volatilized only after a continued blast, and a sublimate is thrown upon the charcoal.

(_a._) _Lead_ (Pb).--This metal occurs in considerable quantity in nature, chiefly as galena or lead-glance (sulphide of lead). Likewise, but more rarely, as a carbonate; also as a sulphate, and sometimes combined with other acids and metals.

In the metallic state, lead is of a bluish-grey color, high lustre, and sp. gr. 11.4. It is soft, and communicates a stain to paper. It is malleable, ductile, but has very little tenacity. It melts at about 612 deg.. Exposed to the air it soon tarnishes, being covered with a grey matter, which some regard as a suboxide (Pb^{2}O), and others as simply a mixture of lead and protoxide. At a glowing heat it is oxidized to a protoxide, and at a white heat it is volatilized. It is insoluble in most acids. It is, however, soluble in nitric acid, but without decomposing water.

(_L._) _Protoxide of Lead_ (PbO).--It is an orange-colored powder, which melts at a glowing temperature, and forms a lamellar mass after cooling. Protoxide of lead absorbs oxygen from the atmosphere while melting, which is given off again by cooling. Being exposed for a longer while to the air, it absorbs carbonic acid and water, and becomes white on the surface. It is soluble in nitric acid and caustic alkalies. It forms with most acids insoluble salts. It is slightly soluble in pure water, but not in water which contains alkaline salts. This hydrate is white.

([beta].) _Red Oxide of Lead_ (PbO^{2}, PbO).--It forms a puce-colored powder. It is insoluble in caustic alkalies. Hydrochloric acid dissolves it and forms a yellow liquid, which is soon decomposed into chloride of lead and chlorine. It is reduced by ignition to the protoxide.

([gamma].) _Peroxide of Lead _(PbO^{2}).--It is a dark-brown powder. It yields with hydrochloric acid the chloride of lead and chlorine gas. When heated it liberates oxygen, and is reduced to the protoxide.

Lead combinations give the following reactions before the blowpipe: Metallic lead tarnishes when heated in the oxidation flame, and is instantly covered with a grey matter, consisting of the protoxide and the metal. It fuses quickly, and is then covered with a yellowish-brown protoxide until all the lead is converted into the protoxide, which melts to a yellow liquid. In the reduction flame and upon charcoal, it is volatilized, while the charcoal becomes covered with a yellow sublimate of oxide. A little distance from the assay, this sublimate appears white (carbonate of lead). Protoxide of lead melts in the flame of oxidation to a beautiful dark yellow bead. In the flame of reduction, and upon charcoal, it is reduced with intumescence to metallic lead, which is volatilized by a continued blast, and sublimates on charcoal, as mentioned above.

Red oxide of lead turns black when heated in the glass tube closed at one end, and liberates oxygen, which is easily detected by the introduction of an ignited splinter, when a more lively combustion of the wood proves the presence of uncombined oxygen. The red oxide in this case is reduced to the protoxide. Heated upon platinum foil, it first turns black, is reduced to the protoxide, and melts into a dark yellow liquid. In the reduction flame, upon charcoal, it is reduced to the metal with intumescence. After a continued blast, a yellow sublimate of protoxide is produced upon the charcoal, and at a little distance off, around this sublimate, a white one of carbonate of lead is produced. This sublimate disappears when touched by the flame of reduction, while it communicates an azure blue-tinge to the external flame. This is likewise the case with the peroxide of lead.

The different oxides of lead produce with the blowpipe reagents the same reactions.

_Borax_ dissolves lead compounds with the greatest readiness upon platinum wire in the oxidation flame to a transparent bead, which is yellow when hot, but colorless after being cooled. With the addition of more of the lead oxide, it becomes opalescent. When heated by the intermittent flame, and with still more of the oxide, it acquires a yellow enamel after cooling. Heated upon charcoal, in the flame of reduction, the bead spreads and becomes opaque. After a continued blast, all the oxide is reduced with effervescence to metallic lead, which melts and runs towards the edges of the bead, while the bead again becomes transparent.

_Microcosmic Salt_ dissolves oxides of lead upon platinum wire in the flame of oxidation easily to a clear, colorless bead, which appears, when highly saturated, yellow while hot. A saturated bead becomes enamel-like after cooling. The bead appears in the flame of reduction, and upon charcoal, of a greyish color and dull. By the addition of more oxide, a yellow sublimate of protoxide is produced upon the charcoal. By the addition of tin, the bead appears of a darker grey, but it is never quite opaque.

_Carbonate of Soda_ dissolves oxide of lead in the flame of oxidation upon platinum wire quite readily to a transparent bead, which becomes yellow when cooling, and is opaque. Upon charcoal in the flame of reduction, it is rapidly reduced to metallic lead, which yields, after a continued blast, a yellow sublimate of oxide upon the charcoal.

(_b._) _Bismuth_ (Bi).--This metal occurs mostly in the metallic state, and less frequently as the sulphide. In the pure metallic state, it is of a reddish-white color and great lustre. It crystallizes in cubes. It is brittle, and may be readily pulverized. It melts at 476 deg., and is volatilized at a white heat. It is soluble in nitric acid, and forms the nitrate of bismuth.

([alpha].) _Oxide of Bismuth _(Bi^{2}O^{3}).--This oxide is a light yellow powder, fusible at a red heat, insoluble in caustic potash and ammonia. It is the base of the salts of bismuth. Its hydrate is white, and easily soluble in acids. The addition of water causes these solutions to become milky, because they are decomposed into a soluble acidulous and an insoluble basic salt of bismuth.

([beta].) _Peroxide of Bismuth_ (BiO^{2}) is a dark-colored powder, completely soluble in boiling nitric acid, and yielding oxygen; produces, with hydrochloric acid, chlorine gas. It can be heated up to the temperature of 620 deg. without being decomposed; but, exposed to a temperature of 630 deg. it yields oxygen. Mixed with combustible substances, it glows with brightness.

([gamma].) _Bismuthic Acid _(Bi^{2}O^{5}) is a brown powder similar to the peroxide, but is converted by boiling nitric acid into a green, scarcely soluble substance (Bi^{2}O^{3}, Bi^{2}O^{5}). Its hydrate is of a red color.

BLOWPIPE REACTIONS.--Metallic bismuth is converted, when exposed upon platinum wire to the flame of oxidation, into a dark brown oxide, which turns light yellow while cooling. It is slowly volatilized when heated, and a yellow sublimate of oxide is produced upon the charcoal.

Oxide of bismuth melts upon platinum foil in the flame of oxidation very easily into a dark-brown liquid, which changes to a light yellow while cooling. By too strong a heat, it is reduced and penetrates the platinum foil.

Upon charcoal, in the flame of oxidation and of reduction, it is reduced to metallic bismuth, which melts into one or more globules. By a continued blast they are slowly volatilized, and produce a yellow sublimate of oxide upon the charcoal, beyond which a white sublimate of carbonate of bismuth is visible. These sublimates disappear in the flame of reduction, but without communicating any color to it.

_Borax_ dissolves oxide of bismuth upon platinum wire, in the flame of oxidation, easily to a clear yellow bead, which appears colorless after cooling. By the addition of more oxide, the hot bead becomes orange. It turns more yellow while cooling, and when cool is opalescent. Upon charcoal in the flame of reduction, the bead becomes turbid and greyish colored. The oxide is reduced with intumescence to the metallic state, and the bead becomes clear again. The addition of tin promotes the reduction.

_Microcosmic Salt_ dissolves oxide of bismuth upon platinum wire, in the flame of oxidation, to a yellow bead, which becomes colorless after cooling. By the addition of more oxide, the bead is yellowish-brown while hot, and colorless after cooling, but not quite transparent. This bead becomes enamelled when heated by the intermittent flame; also, by the addition of still more of the oxide, after it is cooled.

Upon charcoal, in the flame of reduction, and particularly with the addition of tin, the bead is colorless and transparent while hot, but while cooling becomes of a dark-gray color and opaque.

Oxide of bismuth is reduced, by fusion with carbonate of soda, as well in the oxidating as in the reducing flame, instantly to metallic bismuth.

As the above mentioned higher oxides of bismuth are converted by ignition into oxide of the metal and free oxygen, they have the same behavior before the blowpipe.

As bismuth occurs mostly in the metallic form, it is necessary to know how to distinguish it from metals similar to it. Its brittleness distinguishes it from lead, zinc and tin, as they are readily flattened by a stroke of the hammer, while bismuth is broken to pieces. Bismuth, in this latter respect, might perhaps be mistaken for antimony or tellurium; but, by the following examination, it is easy to separate bismuth from antimony or tellurium.

1. Neither bismuth nor antimony sublimates when heated in a glass tube closed at one end. At a temperature which is about to fuse the glass, tellurium yields a small quantity of a white vapor (some tellurium is oxidized to tellurous acid by the oxygen of the air in the tube). After that, a grey metallic sublimate settles on the sides of the tube.

2. Heated in an open tube, antimony yields a white vapor, which coats the inside of the glass tube, and can be driven by heat from one part of the tube to another without leaving a residue. The metallic globule is covered with a considerable quantity of fused oxide. Tellurium produces, under the same circumstances, an intense vapor, and deposits on the glass a white powder, which melts by heat into globules that run over the glass. The metallic globules are covered by fused, transparent, and nearly colorless oxide, which becomes white while cooling. By a high temperature, and with little access of air, metallic tellurium sublimes with the deposition of a grey powder. Bismuth produces, under similar treatment, scarcely any vapor, unless it is combined with sulphur. The metal is enveloped by fused oxide of a dark yellow color, which appears light yellow after being cooled. It acts upon the glass, and dissolves it.

3. Upon charcoal, exposed to the blowpipe flame, the three metals are volatilized, and yield a sublimate upon the charcoal. That of antimony is white, while those of bismuth and tellurium are dark yellow. By exposing them to the flame of reduction, the sublimate of tellurium disappears and communicates an intense green color to the flame. The antimony incrustation gives a feeble greenish-blue color, while the sublimate of bismuth gives no perceptible color in the light. It is, however, worthy of notice that if the operation takes place in the dark, a very pale blue flame will be seen with the bismuth.

(_c._) _Tin_ (Sn).--This metal does not occur in nature in the metallic state, very seldom in the sulphide, but chiefly in the oxide (tinstone). In the metallic state it is silver-white, possesses a very high lustre, is soft (but harder than lead), ductile, but has not much tenacity, and it is very malleable. The metal when it is cast gives a peculiar creaking noise when twisted or bent, which proceeds from the crystalline structure of the metal. This crystallization is quite clearly manifested by attacking the surface of the metal, or that of tin plate, with acids.

Tin is very slightly tarnished by exposure to the air. It fuses at 442 deg., and becomes grey, being a mixture of the oxide and the metal. At a high temperature even, tin is but little subject to pass off as vapor. It is soluble in aqua regia, and with the liberation of hydrogen, in hot sulphuric and hydrochloric acids, and in cold dilute nitric acid, without decomposing water, or the production of a gas, while nitrate of tin and nitrate of ammonia are formed. Concentrated nitric acid converts tin into insoluble tin acids.

([alpha].) _Protoxide of Tin_ (SnO) is a dark-grey powder. Its hydrate is white, and is soluble in caustic alkalies. When this solution is heated, anhydrous crystalline black protoxide is separated. The soluble neutral salts of tin-protoxide are decomposed by the addition of water, and converted into acid soluble, and basic insoluble salts.

When protoxide of tin is ignited with free access of air, it takes fire and is converted with considerable intensity into the acids, producing white vapors. This is likewise the case if it is touched by a spark of fire from steel. The hydrate of the protoxide of tin can be ignited by the flame of a candle, and glows like tinder.

([beta].) _Sesquioxide of Tin_ (Sn^{2}O^{3}) is a greyish-brown powder. Its hydrate is white, with a yellow tinge. It is soluble in aqua ammonia and in hydrochloric acid; this solution forms with solution of gold the "purple of Cassius."

([gamma].) _Stannic Acid_ (peroxide, SnO^{2}).--This acid occurs in nature crystallized in quadro-octahedrons, of a brown or an intense black color, and of great hardness (tinstone). Artificially prepared, it is a white or yellowish-white powder. It exists in two distinct or isomeric modifications, one of which is insoluble in acids (natural tin-acid) while the other (tin-acid prepared in the wet way) is soluble in acids. By ignition the soluble acid is converted into the insoluble. Both modifications form hydrates.

_Reactions before the Blowpipe._--Metallic tin melts easily. It is covered in the flame of oxidation into a yellowish-white oxide, which is carried off sometimes by the stream of air which propels the flame. In the reduction flame, and upon charcoal, melting tin retains its metallic lustre, while a thin sublimate is produced upon the charcoal. This sublimate is light-yellow while hot, and gives a strong light in the flame of oxidation, and turns white while cooling. This sublimate is found near to the metal, and cannot be volatilized in the oxidation flame. In the flame of reduction it is reduced to metallic tin. Sometimes this incrustation is so imperceptible that it can scarcely be distinguished from the ashes of the charcoal. If such be the case, moisten it with a solution of cobalt, and expose it to the flame of oxidation, when the sublimate will exhibit, after cooling, a bluish-green color.

Protoxide of tin takes fire in the flame of oxidation, and burns with flame and some white vapor into tin acid, or stannic acid. In a strong and continued reduction flame, it may be reduced to metal, when the same sublimate above mentioned is visible. The sesquioxide of tin behaves as the above.

Stannic acid, heated in the flame of oxidation, does not melt and is not volatilized, but produces a strong light, and appears yellowish while hot, but changing as it cools to a dirty-yellow white color. In a strong and continued flame of reduction, it may be reduced likewise to the metallic state, with the production of the same sublimate as the above.

_Borax_ dissolves tin compounds in the flame of oxidation, and upon platinum wire, very tardily, and in small quantity, to a transparent colorless bead, which remains clear after cooling, and also when heated intermittingly. But if a saturated bead, after being completely cool, is exposed again to the flame of oxidation, at a low red heat, the bead while cooling is opaque, loses its globular form, and exhibits an indistinct crystallization. This is the case too in the flame of reduction, but if the bead is highly saturated, a part of the oxide is reduced.

_Microcosmic Salt_ dissolves the oxides in the flame of reduction very tardily in a small quantity to a transparent colorless bead, which remains clear while cooling. If to this bead sesquioxide of iron is added in proper proportion, the sesquioxide loses its property of coloring the bead, but of course an excess of the iron salt will communicate to the bead its own characteristic color. In the flame of reduction no further alteration is visible.

Tin-oxides combine with carbonate of soda, in the flame of oxidation upon platinum wire, with intumescence to a bulky and confused mass, which is insoluble in more soda. Upon charcoal, in the reduction flame, it is easily reduced to a metallic globule. Certain compounds of tin-oxides, particularly if they contain tantalum, are by fusion with carbonate of soda reduced with difficulty; but by the addition of some borax, the reduction to the metallic state is easily effected.

Tin-oxides exposed to the oxidation flame, then moistened with a solution of cobalt, and exposed again to the flame of oxidation, will exhibit, after having completely cooled, a bluish-green color.

EIGHTH GROUP.--MERCURY, ARSENIC.

These two metals are volatilized at a temperature lower than that of a red heat, and produce, therefore, no reactions with borax and microcosmic salt. Their oxides are easily reduced to the metallic state.

(_a._) _Mercury_ (Hg).--This metal occurs in nature chiefly combined with sulphur as a bisulphide.

It occurs still more rarely in the metallic form, or combined with silver, selenium, or chlorine.

Mercury, in the metallic state, has a strong lustre, and is liquid at ordinary temperatures, whereby it is distinguished from any other metal. It freezes at 40 deg. and boils at 620 deg., but it evaporates at common temperatures. Pure mercury is unalterable. Upon being exposed to the air, it tarnishes only by admixture with other metals, turns grey on the surface, and loses its lustre. It is soluble in cold nitric acid and in concentrated hot sulphuric acid, but not in hydrochloric acid.

([chi].) _Protoxide of Mercury_ (Hg^{2}O).--It is a black powder, which is decomposed by ignition into metallic mercury and oxygen. By digestion with certain acids, and particularly with caustic alkalies, it is converted into metallic mercury and peroxide. Some neutral salts of the protoxide are only partly soluble in water, as they are converted into basic insoluble and acid soluble salts.

Protoxide of mercury is completely insoluble in hydrochloric acid. Its neutral salts change blue litmus paper to red.

([beta].) _Peroxide of Mercury_ (HgO).--This oxide exists in two allotropic modifications. One is of a brick-red color, and the other is orange. Being exposed to heat, they turn black, but regain their respective colors upon cooling. They are decomposed at a high temperature into metallic mercury and oxygen. They yield with acids their own peculiar salts.

Mercury, in the metallic form, can never be mistaken for any other metal in consequence of its fluid condition at ordinary temperatures.

Exposed to the blowpipe flame, it is instantly volatilized. This is also the case with it when combined with other metals. The oxides of mercury are, in the oxidation and reduction flames, instantly reduced and volatilized. They do not produce any alteration with fluxes, as they are volatilized before the bead melts. Heated with carbonate of soda in a glass tube closed at one end, they are reduced to metallic mercury, which is volatilized, and condenses upon a cool portion of the tube as a grey powder. By cautious knocking against the tube, or by rubbing with a glass rod, this sublimate can be brought together into one globule of metallic mercury. Compounds of mercury can be most completely reduced by a mixture of neutral oxalate of potassa and cyanide of potassium. If the substance under examination contains such a small quantity of mercury that it cannot be distinguished by volatilization, a strip of gold leaf may be attached to an iron wire, and introduced during the experiment in the glass tube. The smallest trace of mercury will whiten the gold leaf in spots.

(_b._) _Arsenic_ (As).--This metal occurs in considerable quantity in nature, chiefly combined with sulphur or metals.

Arsenic, in the metallic state, is of a whitish-grey color, high lustre, and is crystalline, of a foliated structure, and is so brittle that it can be pulverized. It does not melt, but is volatilized at 356 deg.. Its vapor has a strong alliaceous odor. Arsenic sublimes in irregular crystals. By exposure to the air it soon tarnishes, and is coated black. Being mixed with nitrate of potassa and inflamed, it detonates with vehemence. Mixed with carbonate of potassa, it is inflamed by a stroke of the hammer, and detonates violently.

Heated in oxygen gas, it is inflamed, and burns with a pale blue flame to arsenious acid.

([beta].) _Arsenious Acid_ (AsO^{3}).--This acid crystallizes in octahedrons, or, when fused, forms a colorless glass, which finally becomes opaque and enamel-like, or forms a white powder. It sublimes without change or decomposition. When heated for a longer while below the temperature of sublimation, it melts into a transparent, colorless, tough glass. The opaque acid is sparingly soluble in cold water, and still more soluble in hot water. It is converted, by continued boiling, into the transparent acid, which is much more soluble in water. Arsenious acid is easily dissolved by caustic potassa. It is also soluble in hydrochloric acid. This acid occurs associated with antimonious acid, protoxide of tin, protoxide of lead, and oxide of copper. It occurs likewise in very small quantity in ferruginous mineral springs.

([gamma].)_Arsenic Acid_ (AsO^{5}) is a white mass, which readily absorbs moisture and dissolves. It will not volatilize at a low red heat, nor will it decompose. Exposed to a strong heat, it is decomposed, yielding oxygen, and passing into arsenious acid.

_Reactions before the Blowpipe._

Metallic arsenic, heated in a glass tube closed at one end, yields a black sublimate of a metallic lustre, and at the same time gives out the characteristic alliaceous odor. This is the case too with alloys of arsenic, if there is a maximum quantity of arsenic present.

When heated in a glass tube open at both ends, metallic arsenic is oxidized to arsenious acid, which appears as a white crystalline sublimate on the sides of the glass tube. This deposit will occur at some distance from the assay, in consequence of the great volatility of the arsenic. The sublimate can be driven from one place upon the tube to another, by a very low heat. Alloys of arsenic are converted into basic arseniates of metal oxides, while surplus arsenic is converted into arsenious acid, which sublimes on the tube. If too much arsenic is used for this experiment, a dark-brown incrustation will sublime upon the sides of the tube which will give an alliaceous smell. If this sublimate should be deposited near the assay, then it resembles the white sublimate of arsenious acid.

Heated upon charcoal, metallic arsenic is volatilized before it melts, and incrusts the charcoal in the flame of oxidation as a white deposit of arsenious acid. This sublimate appears sometimes of a greyish color, and takes place at some distance from the assay. When heated slightly with the blowpipe flame, this sublimate is instantly driven away, and being heated rapidly in the reduction flame, it disappears with a light blue tinge, while the usual alliaceous or garlic smell may be discerned.

Arsenious acid sublimes in both glass tubes very readily, as a white crystalline sublimate. These crystals appear to be regular octahedrons when observed under the microscope. Upon charcoal it instantly volatilizes, and when heated, the characteristic garlic smell may be observed.

Arsenic acid yields, heated strongly in a glass tube closed at one end, oxygen and arsenious acid, the latter of which sublimes in the cool portions of the tube. Compounds of arsenic produce, in consequence of their volatility, no reactions with fluxes. Being heated upon charcoal with carbonate of soda, they are reduced to metallic arsenic which may be detected by the alliaceous odor peculiar to all the arsenic compounds when volatilized.

NINTH GROUP.--COPPER, SILVER, GOLD.

These metals are not volatile, neither are their oxides. They are reduced to the metallic state, by fusion with carbonate of soda, when they melt to a metallic grain. The oxides of silver and gold are reduced _per se_ to the metallic state by ignition. In the reduction of the oxides of this group, no sublimate is visible upon the charcoal.