Sulphide Sentence Examples
They are precipitated from their alkaline solutions as cobalt sulphide by sulphuretted hydrogen, but this precipitation is prevented by the presence of citric and tartaric acids; similarly the presence of ammonium salts hinders their precipitation by caustic alkalis.
Iridium sulphide, IrS, is obtained when the metal is ignited in sulphur vapour.
It is slightly soluble in potassium sulphide.
The whole of the lead and sulphur of the sulphide was found to be present in the sulphate; in other words, the combining ratio of the lead and sulphur was not altered by the addition of the oxygen.
The most common of these sulphides is cobaltous sulphide, CoS, which occurs naturally as syepoorite, and can be artificially prepared by heating cobaltous oxide with sulphur, or by fusing anhydrous cobalt sulphate with barium sulphide and common salt.Advertisement
Cobalt salts may be readily detected by the formation of the black sulphide, in alkaline solution, and by the blue colour they produce when fused with borax.
Good lodes of stibnite (sulphide of antimony) have been found near Roebourne in Western Australia, but no attempt has yet been made to work them.
Molybdenum, in the form of molybdenite (sulphide of molybdenum), is found in Queensland, New South Wales and Victoria, associated in the parent state with tin and bismuth in quartz reefs.
Zinc ores, in the several varieties of carbonates, silicates, oxide, sulphide and sulphate of zinc, have been found in several of the Australian states, but have attracted little attention except in New South Wales, where special efforts are being made successfully to produce a high-grade zinc concentrate from the sulphide ores.
Cadmium does not occur naturally in the uncombined condition, and only one mineral is known which contains it in any appreciable quantity, namely, greenockite, or cadmium sulphide, found at Greenock and at Bishopton in Scotland, and in Bohemia and Pennsylvania.Advertisement
Cadmium sulphide, CdS, occurs naturally as greenockite (q.v.), and can be artificially prepared by passing sulphuretted hydrogen through acid solutions of soluble cadmium salts, when it is precipitated as a pale yellow amorphous solid.
This precipitate is insoluble in cold dilute acids, in ammonium sulphide, and in solutions of the caustic alkalis," a behaviour which distinguishes it from the yellow sulphides of arsenic and tin.
The difference between these two latter substances was first pointed out by Cronstedt, and in 1778 C. Scheele prepared molybdic acid from the sulphide.
Molybdenum trioxide, Mo03, is prepared by oxidizing the metal or the sulphide by heating them in air, or with nitric acid.
Two oxides of germanium are known, the dioxide, GeO2, being obtained by roasting the sulphide and treatment with nitric acid.Advertisement
By heating the disulphide in a current of hydrogen, germanious sulphide, GeS, is formed.
Sulphur containing selenium, such as occurs in the isle of Vulcano in the Lipari Isles, may be orange-red; and a similar colour is seen in sulphur which contains arsenic sulphide, such as that from La Solfatara near Naples.
Volcanic sulphur usually occurs as a sublimate around or on the walls of the vents, and has probably been formed in many cases by the interaction of sulphur dioxide and hydrogen sulphide.
To obtain pure sulphuretted hydrogen the method generally adopted consists in decomposing precipitated antimony sulphide with concentrated hydrochloric acid.
Azurite occurs with malachite in the upper portions of deposits of copper ore, and owes its origin to the alteration of the sulphide or of native copper by water containing carbon dioxide and oxygen.Advertisement
The problem of the profitable treatment of the sulphide ores has been practically solved here.
Potassium, when heated, burns in the vapour of carbon bisulphide, forming potassium sulphide and liberating carbon.
Ruthenium sulphate, Ru(S04)2, as obtained by oxidizing the sulphide, is an orange-yellow mass which is deliquescent and dissolves in water, the solution possessing a strongly acid reaction.
It is also prepared by digesting precipitated mercuric sulphide with an alkaline sulphide fox some hours; it is said that Chinese vermilion owes its superiority to being made in this way.
We may also notice that thio-ethers combine with alkyl iodides to form sulphide or sulphonium compounds, R3; SI.Advertisement
The mono-benzo-derivatives are coumarone, benzothiophene and indole; the dibenzo-derivatives are diphenylene oxide, dibenzothiophene or diphenylene sulphide, and carbazole.
Sulphur dioxide, recognized by its smell and acid reaction, results from the ignition of certain sulphites, sulphates, or a mixture of a sulphate with a sulphide.
To the filtrate from the aluminium, iron and chromium precipitate, ammonia and ammonium sulphide are added; the precipitate may contain nickel, cobalt, zinc and manganese sulphides.
The precipitate formed by sulphuretted hydrogen may contain the black mercuric, lead, and copper sulphides, dark-brown bismuth sulphide, yellow cadmium and arsenious sulphides, orange-red antimony sulphide, brown stannous sulphide, dull-yellow stannic sulphide, and whitish sulphur, the last resulting from the oxidation of sulphuretted hydrogen by ferric salts, chromates, &c. Warming with ammonium sulphide dissolves out the arsenic, antimony and tin salts, which are reprecipitated by the addition of hydrochloric acid to the ammonium sulphide solution.
The residue from the ammonium sulphide solution is warmed with dilute nitric acid.
Any residue consists of black mercuric sulphide (and possibly white lead sulphate), in which mercury is confirmed by its usual tests.
Filter from the bismuth hydrate, and if copper is present, add potassium cyanide till the colour is destroyed, then pass sulphuretted hydrogen, and cadmium is precipitated as the yellow sulphide.
The next group may contain black nickel and cobalt sulphides, flesh-coloured manganese sulphide, and white zinc sulphide.
The solution with ammonium sulphide gives a white precipitate of zinc sulphide.
It has been suggested that ultramarine is a compound of a sodium aluminium silicate and sodium sulphide.
The putrefaction of the latter sets free sulphuretted hydrogen, which then acts on the iron compounds, precipitating ferrous sulphide.
On the surface, where the sand is bathed by the tidal water, the ferrous sulphide becomes oxidized and the sand is bleached, but underneath it is dense black or grey, as the case may be.
Electrolytes possess the power of coagulating solutions of colloids such as albumen and arsenious sulphide.
Thus neither a chlorate, which contains the ion C103, nor monochloracetic acid, shows the reactions of chlorine, though it is, of course, present in both substances; again, the sulphates do not answer to the usual tests which indicate the presence of sulphur as sulphide.
In other cases the injurious effects of free sulphur are obviated by using instead of it a metallic sulphide, - generally the orange sulphide of antimony; but, for the best results, it is necessary that this should contain from 20 to 30% of uncombined sulphur.
An authority on precious stones, and especially the diamond, he succeeded in artificially making some minute specimens of the latter gem; and on the discovery of radium he was one of the first to take up the study of its properties, in particular inventing the spinthariscope, an instrument in which the effects of a trace of radium salt are manifested by the phosphorescence produced on a zinc sulphide screen.
Galena (q.v.), the principal lead ore, has a world-wide distribution, and is always contaminated with silver sulphide, the proportion of noble metal varying from about o of or less to o 3%, and in rare cases coming up to 2 or i %.
In practice this oxidation process is continued until the whole of the oxygen is as nearly as possible equal in weight to the sulphur present as sulphide or as sulphate, i.e.
At this stage as a rule some rich slags of a former operation are added and a quantity of quicklime is incorporated, the chief object of which is to diminish the fluidity of the mass in the next stage, which consists in this, that, with closed air-holes, the heat is raised so as to cause the oxide and sulphate on the one hand and the sulphide on the other to reduce each other to metal.
Thus, a mixture of lead sulphate (45%) and oxide (44%) with some sulphide (8%), zinc and carbonaceous matter, is agglomerated by a heap-roast and then smelted in a slag-eye furnace with grey slag from the ore-hearth.
Ores are smelted raw if the fall of matte (metallic sulphide) does not exceed 5%; otherwise they are subjected to a preliminary oxidizing roast to expel the sulphur, unless they run too high in silver, say 100 oz.
The leading reverberatory furnace for roasting lead-bearing sulphide ores has a level hearth 14-16 ft.
In making up a charge, the ores and fluxes, whose chemical compositions have been determined, are mixed so as to form out of the components, not to be reduced to the metallic or sulphide state, typical slags (silicates of ferrous and calcium oxides, incidentally of aluminium oxide, which have been found to do successful work).
Pliny mentions it under the name of minium, but it was confused with cinnabar and the red arsenic sulphide; Dioscorides mentions its preparation from white lead or lead carbonate.
Lead sulphide, PbS, occurs in nature as the mineral galena (q.v.), and constitutes the most valuable ore of llead.
Ammonium sulphide blackens it, and it is soluble in solution of ammonium acetate, which distinguishes it from barium sulphate.
But the most delicate precipitant for lead is sulphuretted hydrogen, which produces a black precipitate of lead sulphide, insoluble in cold dilute nitric acid, less so in cold hydrochloric, and easily decomposed by hot hydrochloric acid with formation of the characteristic chloride.
The symptoms of acute poisoning are pain and diarrhoea, owing to the setting up of an active gastro-enteritis, the foeces being black (due to the formation of a sulphide of lead), thirst, cramps in the legs and muscular twitchings, with torpor, collapse, convulsions and coma.
Columbium compounds are usually prepared by fusing columbite with an excess of acid potassium sulphate, boiling out the fused mass with much water, and removing tin and tungsten from the residue by digestion with ammonium sulphide, any iron present being simultaneously converted into ferrous sulphide.
The mother liquor includes generally more or less of nickel, cobalt, zinc and other heavy metals, which, as Wailer showed, can be removed as insoluble sulphides by the addition of ammonium sulphide; uranium, under the circumstances, is not precipitated by this reagent.
Uranyl sulphide, UO 2 S, is a black precipitate obtained by adding ammonium sulphide to a uranyl solution.
If the two reagents are mixed a precipitate of yellow stannic sulphide is produced.
Stannous sulphide, SnS, is obtained as a lead-grey mass by heating tin with sulphur, and as a brown precipitate by adding sulphuretted hydrogen to a stannous solution; this is soluble in ammonium polysulphide, and dries to a black powder.
Stannic sulphide, SnS 2, is obtained by heating a mixture of tin (or, better, tin amalgam), sulphur and sal-ammoniac in proper proportions in the beautiful form of aurum musivum (mosaic gold) - a solid consisting of golden yellow, metallic lustrous scales, and used chiefly as a yellow "bronze" for plaster-of-Paris statuettes, &c. The yellow precipitate of stannic sulphide obtained by adding sulphuretted hydrogen to a stannic solution readily dissolves in solutions of the alkaline sulphides to form thiostannates of the formula M 2 SnS 31 the free acid, H2SnS3, may be obtained as an almost black powder by drying the yellow precipitate formed when hydrochloric acid is added to a solution of a thiostannate.
Stannous salt solutions yield a brown precipitate of SnS with sulphuretted hydrogen, which is insoluble in cold dilute acids and in real sulphide of ammonium, (NH 4) 2 S; but the yellow, or the colourless reagent on addition of sulphur, dissolves the precipitate as SnS 2 salt.
Stannic salt solutions give a yellow precipitate of SnS 2 with sulphuretted hydrogen, which is insoluble in cold dilute acids but readily soluble in sulphide of ammonium, and is re-precipitated therefrom as SnS2 on acidification.
The oil separates from the fat-cells and is found lying free, while the sulphuretted hydrogen evolved as one of the products of putrefaction reacts upon the iron of the blood and throws down a precipitate of sulphide of iron, which in course of time imparts to the limb a range of colour commencing in green and terminating in black.
For example, carbon dioxide occurs in some mines, and hydrogen sulphide, which is a poisonous gas, in others.
Silicon sulphide, SiS 2, is formed by the direct union of silicon with sulphur; by the action of sulphuretted hydrogen on crystallized silicon at red heat (P. Sabatier, Comptes rendus, 1880, 90, p. 819); or by passing the vapour of carbon bisulphide over a heated mixture of silica and carbon.
Neither mechanical nor magnetic concentration can effect much in the way of separation when, as in many complex ores, carbonates of iron, calcium and magnesium replace the isomorphous zinc carbonate, when some iron sulphide containing less sulphur than pyrites replaces zinc sulphide, and when gold and silver are contained in the zinc ore itself.
If the zinc is present as blende, this operation offers considerable difficulties, because in the roasting process the zinc sulphide passes in the first instance into sulphate, which demands a high temperature for its conversion into oxide.
Zinc sulphide, ZnS, occurs in nature as blende (q.v.), and is artificially obtained as a white precipitate by passing sulphuretted hydrogen into a neutral solution of a zinc salt.
In the case of acetate the precipitation is quite complete; from a sulphate or chloride solution the greater part of the metal goes into the precipitate; in the presence of a sufficiency of free HC1 the metal remains dissolved; sulphide of ammonium precipitates the metal completely, even in the presence of ammonium salts and free ammonia.
Acid solutions of titanates are not precipitated by sulphuretted hydrogen; but ammonium sulphide acts on them as if it were ammonia, the sulphuretted hydrogen being liberated.
The metal generally occurs as sulphide of mercury (cinnabar), but the ores vary greatly in richness - from 21 to 20%.
Strontium sulphide, SrS, is formed when the carbonate is heated to redness in a stream of sulphuretted hydrogen.
Aurous sulphide, Au 2 S, is a brownishblack powder formed by passing sulphuretted hydrogen into a solution of potassium aurocyanide and then acidifying.
Sodium aurosulphide, NaAuS 4H 2 O, is prepared by fusing gold with sodium sulphide and sulphur, the melt being extracted with water, filtered in an atmosphere of nitrogen, and evaporated in a vacuum over sulphuric acid.
Sulphuretted hydrogen, obtained by treating iron sulphide or a coarse matte with dilute sulphuric acid, is forced in similarly.
The gold is precipitated as the sulphide, together with any arsenic, antimony, copper, silver and lead which may be present.
In the " dry " methods the silver is converted into sulphide or chloride, the gold remaining unaltered; in the " wet " methods the silver is dissolved by nitric acid or boiling sulphuric acid; and in the electrolytic processes advantage is taken of the fact that under certain current densities and other circumstances silver passes from an anode composed of a gold-silver alloy to the cathode more readily than gold.
The conversion of silver into the sulphide may be effected by heating with antimony sulphide, litharge and sulphur, pyrites, or with sulphur alone.
The oxide, bismuth ochre, Bi 2 O 3, and the sulphide, bismuth glance or bismuthite, are also of commercial importance.
The dry process is more frequently practised, for the easy reducibility of the oxide and sulphide, together with the low melting-point of the metal, renders it possible to effect a ready separation of the metal from the gangue and impurities.
A certain amount of bismuth sulphate is always formed during the calcination; this is subsequently reduced to the sulphide and ultimately to the metal in the fusion.
A dry method of purification consists in a liquation on a hearth of peculiar construction, which occasions the separation of the unreduced bismuth sulphide and the bulk of the other impurities.
Hampe prepared chemically pure bismuth by fusing the metal with sodium carbonate and sulphur, dissolving the bismuth sulphide so formed in nitric acid, precipitating the bismuth as the basic nitrate, redissolving this salt in nitric acid, and then precipitating with ammonia.
Bismuth sulphate, B12(S04)3, is obtained as a white powder by dissolving the metal or sulphide in concentrated sulphuric acid.
The blackish brown sulphide precipitated from bismuth salts by sulphuretted hydrogen is insoluble in ammonium sulphide, but is readily dissolved by nitric acid.
In quantitative estimations it is generally weighed as oxide, after precipitation as sulphide or carbonate, or in the metallic form, reduced as above.
It colours the faeces black owing to the formation of sulphide.
Tantalum forms a sulphide, TaS 2, and two nitrides, TaN 2 and Ta3N5, have been described.
The blue colouring substance is ferrous sulphide, the upper reddish layer contains more ferric oxide, which the predominance of decomposing organic matter in the substance of the mud reduces to ferrous oxide and subsequently by further action to sulphide.
The bottom of the Black Sea is covered by a stiff blue mud in which Sir John Murray found much sulphide of iron,' grains or needles of pyrites making up nearly 50% of the deposit, and there are also grains of amorphous calcium carbonate evidently precipitated from the water.
Under the same conditions it becomes incandescent in the vapour of sulphur, yielding calcium sulphide and carbon disulphide; the vapour of phosphorus will also unite with it at a red heat.
Sulphuretted hydrogen, which is invariably present in commercial acetylene, is formed by the decomposition of aluminium sulphide.
Mourlot has shown that aluminium sulphide, zinc sulphide and cadmium sulphide are the only sulphur compounds which can resist the heat of the electric furnace without decomposition or volatilization, and of these aluminium sulphide is the only one which is decomposed by water with the evolution of sulphuretted hydrogen.
After fusion, the mass is finely powdered and treated with cold dilute hydrochloric acid; and when action has finished, nitric and sulphuric acids are added, the precipitated barium sulphate removed, the liquid distilled and the osmium precipitated as sulphide.
Zirconium combines with sulphur to form a sulphide, and with carbon to form several carbides.
Sodium sulphide, Na 2 S, obtained by saturating a caustic soda solution with sulphuretted hydrogen and adding an equivalent of alkali, is employed in the manufacture of soluble soda glass.
Potassium sulphide, K 2 S, was obtained by Berzelius in pale red crystals by passing hydrogen over potassium sulphate, and by Berthier as a flesh-coloured mass by heating the sulphate with carbon.
It crystallizes in dark red prisms which are readily soluble in water; it is a valuable reagent for the detection of sulphur, this element when in the form of an alkaline sulphide giving a characteristic purple blue coloration with the nitroprusside.
As an alternative test the cyanide may be decomposed by dilute hydrochloric acid, and the liberated hydrocyanic acid absorbed in a little yellow ammonium sulphide.
Chromic sulphide, Cr2S3, results on heating chromium and sulphur or on strongly heating the trioxide in a current of sulphuretted hydrogen; it forms a dark green crystalline powder, and on ignition gives the sesquioxide.
When reduced (in acid solution) they yield amines; distillation with reduced iron gives azo compounds, and warming with ammonium sulphide gives hydrazo compounds.
Magnesium sulphide, MgS, may be obtained, mixed with some unaltered metal and some magnesia, as a hard brown mass by heating magnesia, in sulphur vapour.
At different times propositions have been made to win the metal from its sulphide.
Therefore while less energy is absorbed in its final reduction, more is needed in its initial preparation, and it is questionable whether the economy possible in the second stage would not be neutralized by the greater cost of the first stage in the whole operation of winning the metal from bauxite with the sulphide as the intermediary.
Aluminium sulphide, Al2S3, results from the direct union of the metal with sulphur, or when carbon disulphide vapour is passed over strongly heated alumina.
It is believed that the bluish colour of many clays and limestones is referable to the presence of finely divided pyrites, and it is known that certain deposits of blue mud now forming around continental shores owe their colour, in part, to disseminated iron sulphide.
With sulphur it forms a sulphide which draws together into almost harmless drops, instead of encasing the grains of iron.
The desulphurizing effect of this transfer of the sulphur from union with iron to union with calcium is due to the fact that, whereas iron sulphide dissolves readily in the molten metallic iron, calcium;sulphide, in the presence of a slag rich in lime, does not, but by preference enters the slag, which may thus absorb even as much as 3% of sulphur.
In the former case there is no later chance to remove sulphur, a minute quantity of which does great harm by leading to the formation of cementite instead of graphite and ferrite, and thus making the cast-iron castings too hard to be cut to exact shape with steel tools; in the latter case the converting or purifying processes, which are essentially oxidizing ones, though they remove the other impurities, carbon, silicon, phosphorus and manganese, are not well adapted to desulphurizing, which needs rather deoxidizing conditions, so as to cause the formation of calcium sulphide, than oxidizing ones.
Further, the more sulphur there is to remove, the greater must be the quantity of slag needed to dissolve it as calcium sulphide.
Consequently, when we deoxidize calcium in the iron blastfurnace, it greedily absorbs the sulphur which has been dissolved in the iron as iron sulphide, and the sulphide of calcium thus formed separates from the iron.
In like manner, if the molten iron in the mixer contains manganese, this metal unites with the sulphur present, and the manganese sulphide, insoluble in the iron, slowly rises to the surface, and as it reaches the air, its sulphur oxidizes to sulphurous acid, which escapes.
Beside this their chief and easy work of oxidizing carbon, silicon and phosphorus, the conversion processes have the harder task of removing sulphur, chiefly by converting it into calcium sulphide, CaS, or manganous sulphide, MnS, which rise to the top of the molten metal and there enter the overlying slag, from which the sulphur may escape by oxidizing to the gaseous compound, sulphurous acid, S02.
This sulphide is nearly insoluble in the metal, but is readily soluble in the overlying basic slag, into which it therefore passes.
It is by forming calcium sulphide that sulphur is removed in the manufacture of pig iron in the iron blast furnace, in the crucible of which, as in the electric furnaces, the conditions are strongly deoxidizing But in the Bessemer and open-hearth processes this means of removing sulphur cannot be used, because in each of them there is always enough oxygen in the atmosphere to re-oxidize any calcium as fast as it is deoxidized.
Here sulphur may indeed be removed to a very important degree in the form of manganese sulphide, which distributes itself between metal and slag in rough accord with the laws of equilibrium.
But if we rely on this means we have difficulty in reducing the sulphur content of the metal to 0.03% and very great difficulty in reducing it to 0.02%, whereas with the calcium sulphide of the electric furnaces we can readily reduce it to less than 0.01%.
Characteristic, also, is their action on a photographic plate, and the phosphorescence which they occasion when they impinge on zinc sulphide and some other salts.
Lead plaster (emplastrum lithargyri) boiled in rape oil dissolves, and, sulphide of lead being formed, the oil becomes brown or black.
Other lead compounds give the same black coloration from the formation of sulphide.
The substance is usually optically isotropic, though sometimes it exhibits anomalous double refraction; fibrous zinc sulphide which is doubly refracting is to be referred to the hexagonal FIG.
The mineral is also frequently found massive, with a coarse or fine granular structure and a crystalline fracture; sometimes it occurs as a soft, white, amorphous deposit resembling artificially precipitated zinc sulphide.
Black blende containing ferrous sulphide, in amounts up to 15 or 20% isomorphously replacing zinc sulphide, is known as marmatite (from Marmato near Guayabal in Colombia, South America) and christophite (from St Christophe mine at Breitenbrunn near Eibenstock in Saxony).
In these cases the zinc sulphide has probably arisen from the reduction of sulphate by organic matter.
Lanthanum sulphide, La 2 S 3, is a yellow powder, obtained when the oxide is heated in the vapour of carbon bisulphide.
Thallous sulphide, T1 2 S, is obtained as a black precipitate by passing sulphuretted hydrogen into a thallous solution.
Sulphuretted hydrogen, in the presence of free mineral acid, gives no precipitate; sulphide of ammonium, from neutral solutions, precipitates T12S as a dark brown or black precipitate, insoluble in excess of reagent.
Manganous Sulphide, MnS, found native as manganese glance, may be obtained by heating the monoxide or carbonate in a porcelain tube in a current of carbon bisulphide vapour.
Ammonium sulphide alone gives incomplete precipitation of the sulphide.
This form of the sulphide is readily oxidized when exposed in the moist condition, and is easily decomposed by dilute mineral acids.
Cerous sulphide, Ce2S3, results on heating cerium with sulphur or cerium oxide in carbon bisulphide vapour.
Its principal constituents are always sodium carbonate and calcium sulphide, which are separated by the action of water, the former being soluble and the latter insoluble.
The lixiviation of the blackash requires great care, as the calcium sulphide is liable to be changed into soluble calcium compounds, which immediately react with sodium carbonate and destroy a corresponding quantity of the latter, rendering the soda weaker and impure.
This change of the calcium sulphide may be brought about either by the oxidizing action of the air or by " hydrolysis," produced by prolonged contact with hot water, the use of which, on the other hand, cannot be avoided in order to extract the sodium carbonate itself.
The principal impurities of crude vat-liquor are sodium hydrate and sulphide, the latter of which always leads to the formation of soluble double sulphur salts of sodium and iron.
The operation is finished when all the sodium sulphide has been converted into normal sodium carbonate, partly also into acid sodium carbonate (bicarbonate) NaHCO 3; at the same time a precipitate is formed, consisting of ferrous sulphide, alumina and silica, which is removed by another settling tank, and the clear liquor is now ready either for boiling down in a " fishing-pan " for the manufacture of white soda-ash, or for the process of causticizing.
This " alkali-waste," also called tank-waste or vatwaste, was thrown into heaps where the calcium sulphide was gradually acted upon by the moisture and the oxygen of the air.
The wet alkali-waste as it comes from the lixiviating vats, is transferred into upright iron cylinders in which it is systematically treated with lime-kiln gases until the whole of the calcium sulphide has been converted into calcium carbonate, the carbon dioxide of the lime-kiln gases being entirely exhausted.
Sulphide of carbon is produced here; and there are large dyeworks, and a factory for making bed-stuffing from seaweed.
Thorium sulphide, ThS2, is obtained by burning the metal in sulphur.
It occurs in the uncombined condition and alloyed with iron in meteorites; as sulphide in millerite and nickel blende, as arsenide in niccolite and cloanthite, and frequently in combination with arsenic and antimony in the form of complex sulphides.
When the former is used it is roasted with calcium sulphate or alkali waste to form a matte which is then blown in a Bessemer converter or heated in a reverberatory furnace with a siliceous flux with the object of forming a rich nickel sulphide.
This sulphide is then by further heating converted into the oxide and finally reduced to the state of metal by ignition with carbon in clay crucibles.
The nickel sulphide so obtained is then roasted to oxide and reduced to metal.
Ammonium sulphide precipitates black nickel sulphide, which is somewhat soluble in excess of the precipitate (especially if yellow ammonium sulphide be used), forming a dark-coloured solution.
When prepared by the precipitation of nickel salts with alkaline sulphide in neutral solution it is a greyish black amorphous compound which readily oxidizes in moist air, forming a basic nickel sulphate.
The trisulphide, WS3, is obtained by dissolving the trioxide in ammonium sulphide or by passing sulphuretted hydrogen into a solution of a tungstate and precipitating by an acid in both cases.
It manufactures olive oil, soap, carbon sulphide and playing-cards, and has a large iron foundry.
Copper pyrites, or chalcopyrite, contains 34.6% of copper when pure; but many of the ores, such as those worked specially by wet processes on account of the presence of a large proportion of iron sulphide, contain less than 5% of copper.
The coarse-metal is now smelted, with coke and siliceous fluxes (in order to slag off the iron), and the product, consisting of an impure copper sulphide, is variously known as " blue-metal," when more or less iron is still present, " pimplemetal," when free copper and more or less copper oxide is present, or " fine " or " white-metal," which is a fairly pure copper sulphide, containing about 75% of the metal.
The ores of any economic importance contain the copper either as oxide, carbonate, sulphate or sulphide.
Copper sulphide may be converted either into the sulphate, which is soluble in water; the oxide, soluble in sulphuric or hydrochloric acid; cupric chloride, soluble in water; or cuprous chloride, which is soluble in solutions of metallic chlorides.
Also, however slowly the calcination may be conducted, there is always more or less copper sulphide left unchanged, and some copper oxide formed.
Heap, stall or shaft furnace roasting is not very satisfactory, as it is very difficult to transform all the sulphide into oxide.
The conversion of copper sulphide into the chlorides may be accomplished by calcining with common salt, or by treating the ores with ferrous chloride and hydrochloric acid or with ferric chloride.
Many attempts have been made to use crude sulphide of copper or matte as an anode, and recover the copper at the cathode, the sulphur and other insoluble constitutents being left at the anode.
Cuprous sulphide, Cu 2 S, occurs in nature as the mineral chalcocite or copper-glance, and may be obtained as a black brittle mass by the direct combination of its constituents.
It may be prepared by heating cuprous sulphide with sulphur, or triturating cuprous sulphide with cold strong nitric acid, or as a dark brown precipitate by treating a copper solution with sulphuretted hydrogen.
Cu2S5, Cu 2 S 6, Cu4S5, Cu 2 S 3, have been described; they are all unstable, decomposing into cupric sulphide and sulphur.
In the vicinity there are the most important deposits of zinc and lead in the state, and the city derives its name from the deposits of sulphide of lead (galena), which were the first worked about here; below the galena is a zone of zinc carbonate (or smithsonite) ores, which was the main zone worked between 1860 and 1890; still lower is a zone of blende, or zinc sulphide, now the principal source of the mineral wealth of the region.
Barium hydroxide, Ba(OH) 2, is a white powder that can be obtained by slaking the monoxide with the requisite quantity of water, but it is usually made on the large scale by heating heavy spar with small coal whereby a crude barium sulphide is obtained.
This sulphide is then heated in a current of moist carbon dioxide, barium carbonate being formed, BaS+H 2 O+CO 2 =BaCO 3 +H 2 S, and finally the carbonate is decomposed by a current of superheated steam, BaC03+H20 = Ba(OH) 2 + C02, leavingaresidue of the hydroxide.
Barium chloride, BaCl 2.2H 2 O, can be obtained by dissolving witherite in dilute hydrochloric acid, and also from heavy spar by ignition in a reverberatory furnace with a mixture of coal, limestone and calcium chloride, the barium chloride being extracted from the fused mass by water, leaving a residue of insoluble calcium sulphide.
Barium sulphide, BaS, is obtained by passing sulphuretted hydrogen over heated barium monoxide, or better by fusion of the sulphate with a small coal.
The phosphorescence of the sulphide obtained by heating the thiosulphate is much increased by adding uranium, bismuth, or thorium before ignition pr.
Barium nitrate, Ba(N03)2, is prepared by dissolving either the carbonate or sulphide in dilute nitric acid, or by mixing hot saturated solutions of barium chloride and sodium nitrate.
Antimony, in the form of its sulphide, has been known from very early times, more especially in Eastern countries, reference to it being made in the Old Testament.
Antimony, however, occurs chiefly as the sulphide, stibnite; to a much smaller extent it occurs in combination with other metallic sulphides in the minerals wolfsbergite, boulangerite, bournonite, pyrargyrite, &c. For the preparation of metallic antimony the crude stibnite is first liquated, to free it from earthy and siliceous matter, and is then roasted in order to convert it into oxide.
For rich ores the method of roasting the sulphide with metallic iron is sometimes employed; carbon and salt or sodium sulphate being used to slag the iron.
The primary rocks which appear at Mitushev Kamen are overlaid with thick beds of quartzites and clayslates containing sulphide of iron, with subordinate layers of talc or mica slate, and thinner beds of fossiliferous limestone, Silurian or Devonian.
These bacteria therefore employ SH 2 as their respiratory substance, much as higher plants employ carbohydrates - instead of liberating energy as heat by the respiratory combustion of sugars, they do it by oxidizing hydrogen sulphide.
The filtrate diluted to 200 cc. is carefully neutralized with hydrochloric acid, and excess of 6 cc. of the strong acid is added, and the solution saturated with hydrogen sulphide, which precipitates the copper and cadmium, metals which would otherwise interfere.
Silver sulphide, Ag 2 S, occurs naturally as the orthorhombic acanthite, and the cubic argentite; the telluride, Ag 2 Te, named hessite, assumes cubic forms; other tellurides containing silver are petzite, (Ag,Au) 2 Te, and sylvanite, AuAgTe 4.
In association with antimonious and arsenious sulphides, silver sulphide forms many important minerals, which sometimes present dimorphous forms, reflecting the dimorphism of silver sulphide; moreover, the corresponding arsenious and antimonious compounds are frequently isomorphous.
Sulphuretted hydrogen is decomposed with the formation of a black coating of silver sulphide; this is the explanation of the black tarnish seen when silver is exposed to the fumes of coal gas, and other sulphuretted compounds, such as occur in eggs.
The so-called "oxidized" silver is a copper-silver alloy coated superficially with a layer of the sulphides by immersion in sodium sulphide or otherwise.
In free-milling ore the silver is present either in the native state, or as chloride or as simple sulphide.
This salt, insoluble in water but soluble in brine, also acts upon argentite (Ag 2 S-+-Cu 2 C1 2 =2AgC1±-CuS±-Cu) and pyrargyrite (2Ag 3 SbS 3 -I-Cu 2 C12 = 2AgC1 +Ag 2 S +2Ag +2CuS +Sb2S3), and would give with silver sulphide in the presence of quicksilver, the Patioreaction; metallic silver, cupric sulphide, and mercurous chloride (2Ag 2 S+Cu 2 C1 2 +2Hg=4Ag+2CuS+Hg 2 C1 2), but the iron decomposes the quicksilver salt, setting free the quicksilver.
The European Barrel or Freiberg process consists in roasting the ground ore with salt which converts the silver sulphide into chloride.
The use of sodium hyposulphite as solvent, and sodium sulphide as precipitant, was proposed in 1846 by Hauch and in 1850 by Percy, and put into practice in 1858 by Patera (Patera process); calcium hyposulphite with calcium polysulphide was first used by Kiss in 1860 (Kiss process, now obsolete); sodium hyposulphite with calcium polysulphide was adopted about 1880 by 0.
Silver arsenate and antimoniate are also readily soluble, metallic silver slightly so, silver sulphide not at all.
Silver sulphide falls out as a black mud, with about 50% silver, and the solvent will be regenerated.
If the sodium cuprous hyposulphite was used as a solvent in addition to the simple sodium hyposulphite, cuprous sulphide will be precipitated with the silver sulphide, and the precipitate will be of lower grade.
At some works the silver is precipitated with sodium sulphide, and the liquor, after having been separated from the silver sulphide, is treated with calcium polysulphide, that by the precipitation of calcium sulphate the accumulation of sodium sulphate may be prevented.
The precipitated silver (copper) sulphide is filtered, dried, and usually shipped to silver-lead works to be refined; sometimes it is converted into metallic silver at the works.
On the other hand, silver and silver sulphide are readily amalgamated; and while they are not dissolved in the Patera process, they are in the Russell process.
In principle it consists in oxidizing silver sulphide to the sulphate which is soluble in water, the silver being then precipitable by metallic copper.
This process when carefully carried out, especially as to the details of the roasting process whereby the silver sulphide is oxidized, yields 92% of the silver originally present.
Silver sulphide, Ag 2 S, constitutes the mineral argentite or silver glance, and may be obtained by heating silver with sulphur, or by precipitating a silver salt with sulphuretted hydrogen.
Other minerals, which are not found in commercial quantities, are lead in the form of galena, in Sussex county; graphite, in the crystalline schistose rocks of the Highlands; molybdenum, in the form of a sulphide, in Sussex county; and barytes in Mercer and Sussex counties.
The suggestion made in 1789 by Jean Claude de la Metherie (1743-1817), the editor of the Journal de physique, that this might be done by calcining with charcoal the sulphate of soda formed from salt by the action of oil of vitriol, did not succeed in practice because the product was almost entirely sulphide of soda, but it gave Le Blanc, as he himself acknowledged, a basis upon which to work.
On distillation with phosphorus sulphide it gives cymene.
Phosphorous acid, P(OH) 3, discovered by Davy in 1812, may be ' obtained by dissolving its anhydride, P 4 0 61 in cold water; by immersing sticks of phosphorus in a solution of copper sulphate contained in a well-closed flask, filtering from the copper sulphide and precipitating the sulphuric acid simultaneously formed by baryta water, and concentrating the solution in vacuo; or by passing chlorine into melted phosphorus covered with water, the first formed phosphorus trichloride being decomposed by the water into phosphorous and hydrochloric acids.
Sulphates may be detected by heating the salt mixed with sodium carbonate on charcoal in the reducing flame of the blowpipe; sodium sulphide is thus formed, and may be identified by the black stain produced if the mass be transferred to a silver coin and then moistened.
Another metallic sulphide, blende, ZnS, is of importance for Germany, Belgium and the United States, much less so for the United Kingdom, as a source of sulphur.
The roasting of blende is nothing like so easy as that of pyrites, since the heat developed by the oxidation of the zinc sulphide itself is not sufficient for carrying on the process, and external heat must be applied.
This operation was necessitated by the fact that carbon dioxide has the power of breaking up the sulphur compounds formed by the lime, so that until all carbon dioxide is absorbed with the formation of calcium carbonate, the withdrawal of sulphuretted hydrogen cannot proceed, whilst since it is calcium sulphide formed by the absorption of sulphuretted hydrogen by the slaked lime that absorbs the vapour of carbon disulphide, purification from the latter can only be accomplished after the necessary calcium sulphide has been formed.
In the second box the formation of calcium thiocarbonate takes place by the action of carbon disulphide upon the calcium sulphide with the liberation of sulphuretted hydrogen, which is carried over to the third purifier.
The contents of the third box, being mostly composed of slaked lime, take up sulphuretted hydrogen forming calcium sulphide, and practically remove the remaining impurities, the outlet gas showing 20 grains of sulphuretted hydrogen and 8 grains of carbon disulphide per Ioo cub.
The action of oxide of iron, which has now partly replaced the lime purification, depends on its power of combining with sulphuretted hydrogen to form sulphide of iron.
Upon removing the material from the vessel and exposing it to the atmosphere the sulphide of iron undergoes a revivifying process, the oxygen of the air displacing the sulphur from the sulphide as free sulphur, and with moisture converting the iron into hydrated oxide of iron.
Another black amorphous form results when ferrous salts are precipitated by ammonium sulphide.
It is also prepared by precipitating a ferric salt with ammonium sulphide; unless the alkali be in excess a mixture of ferrous sulphide and sulphur is obtained.
Potassium ferric sulphide, K2Fe2S4, obtained by heating a mixture of iron filings, sulphur and potassium carbonate, forms purple glistening crystals, which burn when heated in air.
Pyrite may be prepared artificially by gently heating ferrous sulphide with sulphur, or as brassy octahedra and cubes by slowly heating an intimate mixture of ferric oxide, sulphur and salammoniac. It is insoluble in dilute acids, but dissolves in nitric acid with separation of sulphur.
When given medicinally preparations of iron have an astringent taste, and the teeth and tongue are blackened owing to the formation of sulphide of iron.
Lower down in the bowel these compounds are converted into ferrous sulphide and tannate, and are eliminated with the faeces, turning them black.
The third theory is that of Bunge, who says that in chlorotic conditions there is an excess of sulphuretted hydrogen in the bowel, changing the food iron into sulphide of iron, which Bunge states cannot be absorbed.
The pentoxide, V205, is obtained when ammonium metavanadate is strongly heated, on calcining the sulphide, or by the decomposition of vanadyl trichloride with water.
The oxide known as white arsenic is mentioned by the Greek alchemist Olympiodorus, who obtained it by roasting arsenic sulphide.
By this method of distillation the arsenic sublimes into the receiver, leaving a residue of iron sulphide in the retort.
In the wet way, arsenious oxide and arsenites, acidified with hydrochloric acid, give a yellow precipitate of arsenic trisulphide on the addition of sulphuretted hydrogen; this precipitate is soluble in solutions of the alkaline hydroxides, ammonium carbonate and yellow ammonium sulphide.
Arsenic is usually estimated either in the form of magnesium pyroarsenate or as arsenic sulphide.
In the sulphide method, the arsenic should be in the arsenious form.
When heated in a current of sulphuretted hydrogen, or carbon bisulphide, it yields a mixture of chromium sesquioxide and sulphide.
The ore is a sulphide, and in 1898 an extensive plant was erected to manufacture sulphuric acid as a by-product.
As some of these substances (for example, lead sulphide and copper pyrites) are readily fusible when first heated, but become more refractory as part of the sulphur is dissipated and oxygen takes its place, it is important that the heat should be very carefully regulated at first, otherwise the mass may become clotted or fritted together, and the oxidizing effect of the air soon ceases unless the fritted masses be broken small again.
He showed that lead sulphide, a black substance containing only lead and sulphur, could be converted by oxidation into lead sulphate, a white compound containing oxygen as well as lead and sulphur.
After studying at Marburg under Hermann Kolbe and at Heidelberg under Robert Bunsen, he came to England in 1862 and obtained a position in a chemical works at Widnes, where he elaborated the practical application of a method he had devised for recovering the sulphur lost as calcium sulphide in the black ash waste of the Leblanc alkali process.
Kiihne (D.R.P. 147,871) described a process in which external heating is not necessary, a mixture of aluminium turnings, sulphur and boric acid being ignited by a hot iron rod, the resulting aluminium sulphide, formed as a by-product, being decomposed by water.
It is still the commonest detonator, but it is now usually mixed with other substances; the British service uses for percussion caps 6 parts of fulminate, 6 of potassium chlorate and 4 of antimony sulphide, and for time fuses 4 parts of fulminate, 6 of potassium chlorate and 4 of antimony sulphide, the mixture being damped with a shellac varnish; for use in blasting, a home office order of 1897 prescribes a mixture of 4 parts of fulminate and 1 of potassium chlorate.
In many instances it has been replaced by mechanical furnaces, which are now common in roasting sulphide copper ores (see Sulphuric AcID).
The chief ore is zinc blende, or sphalerite (see Blende), which generally contains, in addition to zinc sulphide, small amounts of the sulphides of iron, silver and cadmium.
The first process never extracts all the bismuth, as much as onethird being retained in the matte or speiss; the second is more satisfactory, since the extraction is more complete, and also allows the addition of reducing agents to decompose any admixed bismuth oxide or sulphide.
When digested with fuming hydrochloric acid for some time it is converted into ad furfurane dicarboxylic acid (see Furfurane); while on heating with barium sulphide it is transformed into a - thiophene carboxylic acid (see Thiophene).
Electrolytic methods, in which a solution of antimony sulphide in sodium sulphide is used as the electrolyte, have been proposed (see German Patent 67973, and also Borcher's Electro-Metallurgie), but do not yet appear to have been used on the large scale.
Antimony and its salts may be readily detected by the orange precipitate of antimony sulphide which is produced when sulphuretted hydrogen is passed through their acid solutions, and also by the Marsh test (see Arsenic); in this latter case the black stain produced is not soluble in bleaching powder solution.
Cobalt chloride, CoC1 2, in the anhydrous state, is formed by burning the metal in chlorine or by heating the sulphide in a current of the same gas.
The term allotropy has also been applied to inorganic compounds, identical in composition, but assuming different crystallographic forms. Mercuric oxide, sulphide and iodide; arsenic trioxide; titanium dioxide and silicon dioxide may be cited as examples.