Sulfate of iron

“ This device not only makes the cast iron much more uniform, but also removes much of its sulphur by a curious slow reaction. Many metals have the power of dissolving their own oxides and sulphides, but not those of other metals. Thus iron, at least highly carburetted, i.e. cast iron, dissolves its own sulphide freely, but not that of either calcium or manganese. Consequently, when we deoxidize calcium in the iron blast-furnace, 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 the arts, as sulphate of iron (copperas) , it is extensively used in dyeing, and for various other purposes. The dried sulphate (ferri sulphus exsiccatum) is chiefly used to make pills.
Crude sulphate of iron is frequently contaminated with the sulphates of copper, zinc, manganese, aluminium, magnesium, and calcium, which, with the exception of the first, are removed with difficulty. It also contains variable proportions of the neutral and basic ferric sulphates. The preparation obtained by direct solution of iron in dilute sulphuric acid should, therefore, be alone used in medicine. ”

“ The washed sample is then fused in the usual way to determine the proportion of sulphur existing as iron pyrites. The distinction between sulphur present as sulphate and sulphide is of importance in the examination of coals intended for iron smelting, as the sulphates of the earthy metals are reduced by the gases of the furnace to sulphides, which pass into the slag without affecting the quality of the iron produced, while the sulphur of the metallic sulphides in the ash acts prejudicially upon the metal. ”

“ The sulphate of iron is the starting point in preparing all the compounds of iron which are used in medicine, and it is important therefore, to know how to separate easily the impurities which are contingent to this extremely cheap article of commerce. ”

“ Where beds of common iron pyrites occur, the iron sulphide is converted into sulphate by exposure to the oxidising influence of the air. The result is an acid sulphate of iron, which is leached out and neutralised by addition of more iron in the form of scrap. The neutral sulphate is crystallised out of the liquor, and calcined in a muffle furnace, the shade of the ultimate product being governed by the degree or duration of the roasting. ”

“ If exposed to a sudden, though gentle heat, by holding it, for instance, in a hand when that is warm, it will sometimes break in pieces with a crackling noise.
145It is a remarkable circumstance, that, if a bar of iron be heated to perfect whiteness, and then touched with a roll of sulphur, the two bodies combine, and drop down together, in a fluid state, forming what is called sulphuret of iron, a compound of the same nature as iron pyrites (236) . ”

“ Corresponding to ferrous oxide and ferric oxide, respectively, are two series of iron salts, ferrous salts and ferric salts.
The action of acids on metallic iron, in the absence of oxidizing agents, causes the formation of ferrous salts, among which deserve mention the sulphate, the sulphide, the chloride, and the oxalate. Ferrous sulphate, known as green vitriol, or iron vitriol, is the substance from which the compounds of iron are generally prepared. ”

“ Metallic sulphides when fused with an excess of nitre are completely oxidised. If the ore is rich in sulphur, some inert body (such as sodium chloride, or, better, sodium carbonate) is added to dilute the action. With pure sulphur, the action is so energetic as to cause an explosion, so that care should be taken. With burnt ores (incompletely calcined pyrites) , there is sufficient oxide of iron present to prevent too rapid action. ”

“ The iron in water from old coal pits and shale deposits is usually present as sulphate due to the oxidation of pyrites, a sulphuret or sulphide of iron. Water from heaths and moorlands is often acid from certain vegetable acids termed "peaty acids." This acidity places the water in the condition of a direct solvent for iron, and that dissolved iron may cause great injury. If such water cannot be dispensed with, the best way is to carefully neutralise it with carbonate of soda ”

“ The action of diluted sulphuric acid on metals closely resembles that of dilute hydrochloric acid. Magnesium, aluminium, iron, zinc, nickel, cobalt, manganese, and cadmium dissolve, with evolution of hydrogen, in the cold acid, or when warmed. The action of hot and strong sulphuric acid is [Pg 59] altogether different; it acts as an oxidising agent, and is itself reduced to sulphur dioxide or even to sulphur. The following metals are attacked in this way:—copper, bismuth, mercury, silver, antimony, tin, and lead. Gold, platinum, and arsenic are not affected. ”

“ Copper sulphate is nearly as active, and is followed by zinc sulphate and cadmium sulphate. Lead acetate and nitrate, in a one-percent solution, only delay decay, while it is prevented by the same strength of iron sulphide. ”

“ Iron is one of the most timid of metals. It has a great disinclination to be alone. It is also one of the most altruistic of the elements. It likes almost every other element better than itself. It has an especial affection for oxygen, and, since this is in both air and water, and these are everywhere, iron is not long without a mate. The result of this union goes by various names in the mineralogical and chemical worlds, but in common language, which is quite good enough for our purpose, it is called iron rust. ”

“ The residuary impure black oxide is mixed with as much sulphuric acid (concentrated) as will make it into a paste, which is exposed at first to a moderate heat, then to a cherry-red ignition for an hour. The sulphate thus obtained is reduced to powder, and dissolved in water. To the solution, carbonate of potash is gradually added, in order to separate the remaining portion of oxide of iron; the quantity of which depends upon the previous degree of calcination. If it be not enough oxidized, the iron is difficult to be got rid of. ”

“ The result is a bluish colored mixture, soon changing to olive green. If the sulphate of iron be not properly selected, or if it be rubbed in the mortar, as inferred from the formula, the mixture is more or less brown and proportionably deteriorated. Of course, we should not “take sulphate of iron in powder.” {44}
In giving directions for making a compound, something, certainly, is to be expected from the knowledge and skill of the manipulator. ”

“ Water saturated with fixed air dissolves iron, and makes a pleasant chalybeat.
The calx of iron gives a green colour to glass.
[Pg 107] Iron readily combines with sulphur. When they are found combined by nature, the substance is called pyrites.
The union of phosphoric acid with iron makes it brittle when cold, commonly called cold short; and the union of arsenic makes it brittle when hot, thence called red short.
Iron unites with gold, silver, and platina, and plunged in a white heat into mercury, it becomes coated with it ”

“ During the melting of the charge the heat is kept as high as possible and the molten iron is “puddled,” i. e., stirred, by the “puddler” or his helper with a “rabbler” or iron bar. In order to take out the phosphorus and sulphur, which for best results should be removed before the carbon is eliminated, the heat of the furnace is lowered somewhat as soon as all of the pig has melted, and some iron oxide is mixed into the “bath” of molten iron and cinder. Most of the phosphorus and sulphur are chemically acted upon and pass into the cinder which covers the iron. ”

“ When strongly heated iron inflames in oxygen and in sulphur vapour; it also combines directly with the halogens. It dissolves in most dilute acids with liberation of hydrogen; the reaction between sulphuric acid and iron turnings being used for the commercial manufacture of this gas. It dissolves in dilute cold nitric acid with the formation of ferrous and ammonium nitrates, no gases being liberated; when heated or with stronger acid ferric nitrate is formed with evolution of nitrogen oxides. ”

“ Water and carbon dioxide are objectionable only as they replace the iron, while the others exert an influence upon the fluxing properties of the ore and the course of smelting operations. Of greater importance, however, are the small quantities of phosphorus, sulphur, and titanium, these impurities being almost wholly obnoxious in their effect. Phosphorus gives a fluid pig iron that can be converted into steel only by employing special methods of treatment. ”

“ Iron is, no doubt, very abundant in nature; but it is always mixed with some other substance that not only renders it unfit for use, but hides its qualities. It is found in the state of what is called iron-stone, or iron-ore. Sometimes it is mixed with clay, at other times with lime or with the earth of flint; and there are also cases in which it is mixed with sulphur. In short, in the state in which iron is frequently met with, it is a much more likely substance to be chosen for paving a road, or building a wall, than for making a knife. ”

“ The fuel has, in addition to its duties of deoxidizing and carburizing the iron and yielding the heat needed for melting both the iron and slag, the further task of desulphurizing the iron, probably by the reaction FeS + CaO + C = Fe + CaS + CO.
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. ”

“ When the iron is present as bicarbonate, it acts on soap solutions like the analogous lime and magnesia compounds, producing even worse results. In wool scouring, cotton bleaching, and other processes requiring the use of alkaline carbonates, ferric oxide is precipitated on the fibre. A yellowish tinge is communicated to bleached fabrics, and to dye bright and light colours is rendered almost out of the question. You may always suspect iron to be present in water flowing from or obtained directly out of old coal pits, iron mines, or from places abounding in iron and aluminous shales. ”

“ Chemists say that if a bed of fixed earthy sulphur be combined with fixed earthy quicksilver, and the two together are neither pure white but of a livid whiteness, if the sulphur prevail, iron is formed. For these stern masters of metals who by many inventions twisting them about, pound, calcine, dissolve, sublime, and precipitate, decide that this metal, both on account of the earthy sulphur and of the earthy mercury, is more truly a son of the earth than any other; they do not even think gold or silver, lead, tin, or copper itself so earthy ”

“ That's a good idea, Dave. I might use a sulphide—nearly all sulphides are colored, and form very easily and rapidly. Or I might use liquid ozone. That will tarnish almost anything to an oxide, which is also apt to be colored. I could certainly heat the ship that way, but I wonder—I'm afraid that the oxide or sulphide would break down too easily. There is only one metal that they might use on which that would work, namely steel. Iron sulphide is black, stable, and will not decompose readily. ”

“ But if sufficient quantities of iron are taken internally, the alkaline sulphides are decomposed and the organic iron of the food becomes available. The amounts of iron required depend of course upon the amount of alkaline sulphides in the intestines, and this is why it may be found necessary to administer as much as 18 grains a day to an anæmic woman whose body, in a normal state, contains altogether about 30 grains. ”

“ The sulphur may be present as sulphide or sulphate.
Arsenic.—Take 5 grams, and evaporate with nitric acid; dilute, add ammonia, pass sulphuretted hydrogen, and filter. [Pg 287]
To the filtrate add "magnesia mixture." Collect the precipitate, ignite with nitric acid, and weigh as magnesic pyrarsenate.
The following may be taken as an example of the composition of an impure black tin:—
Examination of Hardhead.—In the smelting of tin ores a quantity of speise, known as "hardhead," is produced. It is essentially an arsenide of iron, carrying a considerable quantity of tin. ”

“ It occurs in nature as the mineral melanterite, either crystalline or fibrous, but usually massive; it appears to have been formed by the oxidation of pyrite or marcasite. It is manufactured by piling pyrites in heaps and exposing to atmospheric oxidation, the ferrous sulphate thus formed being dissolved in water, and the solution run into tanks, where any sulphuric acid which may be formed is decomposed by adding scrap iron. By evaporation the green vitriol is obtained as large crystals. ”

“ Both sulphur and selenium may be thrown into several curious states, which chemists conveniently dispose of by calling them allotropic, a term freely used when they are puzzled to know what has happened. The chemical and physical history of iron, again, is full of anomalies; not only does it undergo inexplicable changes of hardness and texture in its alloys with carbon and other elements, but it is almost the only substance which conveys sound with greater velocity at a higher than at a lower temperature, the velocity increasing from 20° to 100° C., and then decreasing. ”