Iron(II) sulfate

“ Sulphur Compounds.—Ferrous sulphide, FeS, results from the direct union of its elements, best by stirring molten sulphur with a white-hot iron rod, when the sulphide drops to the bottom of the crucible. It then forms a yellowish crystalline mass, which readily dissolves in acids with the liberation of sulphuretted hydrogen. Heated in air it at first partially oxidizes to ferrous sulphate, and at higher temperatures it yields sulphur dioxide and ferric oxide. It is unaltered by ignition in hydrogen. An amorphous form results when a mixture of iron filings and sulphur are triturated with water. ”

“ 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. ”

“ 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. ”

“ 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. ”

“ 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. ”

“ SULPHATE OF IRON. Also called “Green Vitriol” and “Green Copperas,” is a combination of sulphuric acid and oxide of iron, and may be made by putting iron filings or pieces of iron into a mixture of sulphuric acid and water, and when all action has ceased evaporating the liquid, and setting it by till crystals form—these are of a pale green color. The sulphate of iron of commerce is formed by exposing the iron pyrites found in the coal districts to the air till it falls to powder; water is then poured over this substance, and the fluid collected and evaporated. ”

“ 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. ”

“ 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 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 ”

“ 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. ”

“ 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. ”

“ 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.
The conversion into sulphate is generally effected by the oxidizing processes of weathering, calcination, heating with iron nitrate or ferric sulphate. It may also be accomplished by calcination with ferrous sulphate, or other easily decomposable sulphates, such as aluminium sulphate. Weathering is a very slow, and, therefore, an expensive process ”

“ Combined with metals (sulphides) , it is common in all mineral districts. Iron pyrites (FeS2) is the most abundant source of this element. Sulphates, such as gypsum, are fairly common, but have no value so far as the sulphur in them is concerned. In coal it exists as an impurity, occurring partly as a constituent of organic compounds.
Sulphur, whether free or combined with metals, forms, on burning, sulphurous oxide (SO2) , which by the action of oxidising agents and water is converted into sulphuric acid. ”

“ 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. ”

“ The explanation is, that the waste pyrites 'contained not only sulphide of iron and earthy constituents, but also sulphide of zinc, and that by the influence of the oxygen of the atmosphere and the presence of water, these sulphides were gradually converted into the corresponding sulphates;' and these, continually extracted by the{751} rain-water, soaked into the soil, contaminated the wells, and produced other injurious effects.
The want of really efficient names to distinguish various kinds of manufactured iron has long been felt in the iron trade. ”

“ It is largely used in the laboratory as a source of sulphuretted hydrogen. The hydrated sulphide is a black, insoluble substance, rapidly decomposed by exposure to the air. Proposed by Mialhe as an antidote to the salts of arsenic, antimony, bismuth, lead, mercury, silver, and tin, and to arsenious acid; more especially to white arsenic and corrosive sublimate. A gargle containing a little hydrated sulphide of iron will instantly remove the metallic taste caused by putting a little corrosive sublimate into the mouth. ”

“ Precipitation with sulphur dioxide and sulphuretted hydrogen proceeds much more rapidly, and has been adopted at many works. Sulphur dioxide, generated by burning sulphur, is forced into the solution under pressure, where it interacts with any free chlorine present to form hydrochloric and sulphuric acids. 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. ”

“ The effects of oxidation may be seen in the alteration of many kinds of rocks and in red and yellow colors of soils and subsoils.
Pyrite is a very hard mineral of a pale brass color, found in scattered crystals in many rocks, and is composed of iron and sulphur (iron sulphide) . Under the attack of the weather it takes up oxygen, forming iron sulphate (green vitriol) , a soluble compound, and insoluble hydrated iron oxide, which as a mineral is known as limonite. Several large masses of iron sulphide were placed some years ago on the lawn in front of the National Museum at Washington. ”

“ 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. ”

“ Sulphur is now generally regarded as emanating from the stage of intermittent lethargy of a volcano, and the sulphides of iron, copper, arsenic, zinc, selenium, etc., fall in the same category as sulphur; they are secondary, not primary, formations. In the stage further off we have the host of sulphates produced by the oxidation of the sulphur into sulphuric acid, and its subsequent reaction on the metals and earths with which it becomes associated. ”

“ 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. ”

“ 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) . ”

“ Thus a rotten egg emits sulphuretted hydrogen. Sulphur occurs largely in nature, as the various insoluble sulphides of the metals. Iron, copper, zinc, lead, antimony, arsenic, &c., occur in nature combined with sulphur. These sulphides frequently have a metallic lustre, and in the majority of cases occur crystallised, [202] and also very often several sulphides occur combined or mixed together in these crystalline compounds. If they are yellow and have a metallic lustre they are called pyrites. ”

“ Many mineral springs owe their medicinal properties to the hydrosulphuric acid which they contain, and whose decomposition frequently gives rise to the formation of sulphur. When the large marble slab which covers the imperial source at Aix-la-Chapelle is removed at the end of every twenty years, about two hundred pounds of sulphur are collected from the walls above the spring.
Combinations of sulphur with metals, particularly with iron and copper (pyrites) , occur in much more considerable masses and in a far greater number of localities than the pure uncombined mineral. ”

“ The value of limestone as a flux depends upon its freedom from impurities, such as silicon and sulphur.
Sulphur and phosphorus are two elements which must be kept out of the product. When there is too much sulphur, the iron is exceedingly brittle at a dull red heat, although it can be worked at a higher or lower temperature. It is called red-short iron and makes welding difficult. With steel, sulphur diminishes the tensile strength and ductility. If there is too much phosphorus combined with iron, the metal will crack when hammered cold. ”

“ 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. ”

“ The sulphides of iron and manganese, &c., are very easily oxidised in this manner. But if these hydrates be ignited, they lose their water (the ignition must be carried on in a stream of hydrogen to prevent their oxidation during the process) , become denser, and are no longer oxidised at the ordinary temperature. Those sulphides whose corresponding sulphates are decomposed by heat part with their sulphur in the form of sulphurous anhydride when they are ignited in air, and the metal, as a rule, remains behind as oxide. ”