Silicon fluoride is evolved, and, if a moistened gla.s.s rod is held in the tube, it becomes coated with a white deposit of silica, formed by the decomposition of the silicon fluoride by the water. This is also used as a test for silica; but in this case the substance is mixed with a fluoride, and the experiment must obviously be carried out in a platinum vessel.
~Separation and Determination.~--The determination of fluorine is difficult. In the case of fluorides free from silicates (such as fluor-spar), it is determined indirectly by decomposing a weighed portion with sulphuric acid, evaporating, igniting, and weighing the residual sulphate. The increase in weight multiplied by 0.655 gives the weight of fluorine.
In the presence of silica this method does not answer, because of the volatilisation of silicon fluoride. In these cases Wohler adopted the following plan, which resembles that for the indirect determination of carbon dioxide. Mix the weighed substance in a small flask with powdered silica and sulphuric acid. The mouth of the flask is closed with a cork carrying a tube which is filled, the first half with calcium chloride and the second half with pumice coated with dried copper sulphate. The apparatus is weighed quickly, and then warmed till decomposition is complete. A current of dry air is aspirated for a minute or two; and the apparatus again weighed. The loss in weight gives that of the silicon fluoride (SiF_{4}), which, multiplied by 0.7307, gives the weight of fluorine.
Fresenius uses the same reaction; but collects and weighs the silicon fluoride. The finely powdered and dried substance is mixed with ten or fifteen times its weight of ignited and powdered silica. The mixture is introduced into a small dry flask connected on one side with a series of drying-tubes, and on the other with an empty tube (to condense any sulphuric acid). To this last is joined a drying-tube containing chloride of calcium and anhydrous copper sulphate. This is directly connected with a series of three weighed tubes in which the fluoride of silicon is collected. The last of these is joined to another drying-tube. The first weighed tube contains pumice and cotton wool, moistened with water; the second tube contains soda-lime as well as (in the upper half of the second limb) fused calcium chloride between plugs of wool; the third tube is filled half with soda-lime and half with fused calcium chloride. The distilling-flask containing the substance mixed with silica is charged with 40 or 50 c.c. of sulphuric acid, and placed on the hot plate. Alongside it is placed a similar dry flask containing a thermometer, and the temperature in this is kept at 150 or 160 C. A current of air is sent through the tubes during the operation, which takes from one to three hours for from 0.1 to 1 gram of the substance. A correction is made by deducting 0.001 gram for every hour the dried air has been pa.s.sed through. The increase in weight of the three tubes gives the weight of the silicon fluoride.
Penfield uses a similar arrangement, but pa.s.ses his silicon fluoride into an alcoholic solution of pota.s.sium chloride. Silica and pota.s.sium silico-fluoride are precipitated, and hydrochloric acid is set free.[100] The acid thus liberated is t.i.trated, with a standard solution of alkali, in the alcoholic solution, and from the amount of free acid found the fluorine is calculated. The weight of hydrochloric acid (HCl) found, multiplied by 1.562, gives the weight of the fluorine. With this method of working, fewer ~U~-tubes are required. The exit tube from the flask is bent so as to form a small ~V~, which is kept cool in water; this is directly connected with the ~U~-tube containing the alcoholic solution of pota.s.sium chloride. The flask with the a.s.say is heated for about two hours, and a current of dry air is aspirated throughout the determination. Fluoride of silicon is a gas not easily condensed to a liquid: but is immediately decomposed by water or moist air.
FOOTNOTES:
[95] This will require two or three hours to thoroughly complete. It is best to powder the oxide first produced, and recalcine.
[96] No magnetic oxide was formed.
[97] For example:--
CaO + 2HCl = CaCl_{2} + H_{2}O.
PbO + H_{2}SO_{4} = PbSO_{4} + H_{2}O.
MgO + 2HNO_{3} = Mg(NO_{3})_{2} + H_{2}O.
Al_{2}O_{3} + 6HCl = Al_{2}Cl_{6} + 3H_{2}O.
Fe_{2}O_{3} + 3H_{2}SO_{4} = Fe_{2}(SO_{4})_{3} + 3H_{2}O.
[98] Fe_{2}O_{3}: 2FeO:: 0.2877: 0.2589.
[99] 100 c.c. contain 1 gram of sulphuric acid.
[100] 3SiF_{4} + 4KCl + 2H_{2}O = 2K_{2}SiF_{6} + SiO_{2} + 4HCl.
CHAPTER XVI.
SULPHUR AND SULPHATES.
Sulphur occurs native in volcanic districts, and is mined in Sicily, Italy, and California in considerable quant.i.ties. Combined with metals (sulphides), it is common in all mineral districts. Iron pyrites (FeS_{2}) 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 const.i.tuent of organic compounds.
Sulphur, whether free or combined with metals, forms, on burning, sulphurous oxide (SO_{2}), which by the action of oxidising agents and water is converted into sulphuric acid. It forms two oxides, sulphurous (SO_{2}) and sulphuric (SO_{3}), which combine with bases to form sulphites and sulphates. Sulphites are of little importance to the a.s.sayer, and are converted into sulphates by the action of nitric acid and other oxidising agents.
The native sulphides, when acted on with hydrochloric acid, give off sulphuretted hydrogen; with nitric acid or aqua regia, sulphates are formed, and more or less sulphur separated.
Sulphur is detected in sulphides by the irritating odour of sulphurous oxide given off on roasting, by the evolution of sulphuretted hydrogen when treated with hydrochloric acid, or by a white precipitate of barium sulphate formed when barium chloride is added to the aqua regia solution.
~Dry a.s.say.~--There is no method of general application. Free or native sulphur may be volatilised, condensed, and weighed, but pyrites only gives up a portion of its sulphur when heated in a closed vessel, while most sulphides, and all sulphates, give up none at all.
In the determination of sulphur in brimstone, 10 grams of the substance are taken, placed in a small porcelain dish, heated over a Bunsen burner in a well-ventilated place, and ignited. When the sulphur has been completely burnt off, the residue (which consists chiefly of sand) is collected and weighed. In a separate portion the moisture and a.r.s.enic are determined; the amounts of these are deducted from the loss in the first experiment. The difference, multiplied by 10, gives the percentage of sulphur.
WET METHODS.
~Solution.~--All sulphates, excepting those of lead, barium, strontium, and lime, are soluble in water or dilute acid. All sulphides, except cinnabar, are converted into sulphates by the action of nitric acid at a gentle heat; or, better, by the action of a mixture of three volumes of nitric acid and one volume of hydrochloric acid. This last attacks cinnabar as well. With most substances it is difficult to convert the whole of the sulphur into sulphuric acid. The sulphur separates out at first as a dark spongy ma.s.s, which (on continued treatment) changes to light-coloured flakes. When the solution becomes concentrated and the temperature rises sufficiently, the sulphur fuses into one or more honey-coloured globules which, owing to the small surface they oppose to the acid, are very slowly oxidised. It is not desirable to a.s.sist the formation of these globules; therefore, the temperature is kept as low as possible, and strong nitric acid is used. When such globules form, it is best to allow the solution to cool, when the globules will solidify.
They can then be filtered off and picked out from the insoluble residue, dried, weighed, ignited, and again weighed, the loss being counted as sulphur. With iron pyrites this difficulty seldom occurs.
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.
These fusions with nitre are best conducted in a platinum dish covered with a piece of platinum foil. The ore is ground with the nitre to ensure complete mixing. The heat need not be excessive, so that a single Bunsen burner placed beneath the dish will suffice; if the bottom of the dish is seen to be red-hot, it is sufficient. On cooling and extracting with water, the sulphur will pa.s.s into solution as pota.s.sium sulphate, which is then filtered off from the insoluble oxides of iron, copper, &c. The filtrate, after having been treated with a large excess of hydrochloric acid, evaporated to dryness, and re-dissolved in water, is ready for the determination.
Lead sulphate may be dissolved by boiling with ammonium acetate. The insoluble sulphates of barium, strontium, and lime, are decomposed by fusing with 4 or 5 times their weight of "fusion mixture." The alkaline sulphates are then dissolved out with water, and filtered off from the insoluble residue. The filtrate is rendered acid with hydrochloric acid.
~Separation.~--The determination of the sulphuric acid in these solutions by precipitation with barium chloride also serves as a separation; but in hot acid solutions containing copper, and more especially iron salts, the baric sulphate has a strong tendency to carry down amounts of those bodies, varying, no doubt, with the conditions of the precipitation. Boiling hydrochloric acid fails to completely extract them. Moreover, the use of hot concentrated hydrochloric acid causes a loss by dissolving barium sulphate. Nitric acid and nitrates must be decomposed by prolonged boiling and evaporation with hydrochloric acid.
The iron may be removed by adding a slight excess of ammonia to the faintly acid solution, filtering off, and washing the precipitated ferric hydrate with hot water. By slightly acidulating the filtrate with hydrochloric acid, it will be rendered ready for the determination.
GRAVIMETRIC METHOD.
This a.s.say is one of those which strikingly shows the necessity of getting the a.s.say solution under proper conditions, in order to obtain satisfactory results. The method has been repeatedly investigated, and the conclusion arrived at, "that it can be correct only by accident."
Yet there are many chemists who get good results, and place considerable faith in its accuracy. This can only be due to differences in the manner of working. It is generally understood that nitric acid or nitrates must be absent; and our experience fully confirms this. Precipitations in nitrate solutions are worthless, as the following experiments show. In each experiment the bulk of the solution was 150 c.c. The solutions contained 10 grams of nitre, were freely acid with hydrochloric acid, and were precipitated (while boiling) with slight excess of baric chloride.
Sulphuric acid taken 0.020 gram 0.050 gram 0.100 gram " found 0.019 " 0.047 " 0.098 "
" taken 0.500 " 1.004 " 1.000 "
" found 0.526 " 1.126 " 1.126 "
All the precipitates were boiled with hydrochloric acid, and thoroughly washed before weighing. The results of some other experiments on this subject are given under "sulphur" in the "examination of commercial copper," page 207.
The solution having been obtained free from nitrates and chlorates (and containing but little free hydrochloric acid), is largely diluted, heated to boiling, and precipitated with a moderate excess of a solution of chloride of barium (8 parts of the crystallized barium chloride are sufficient for 1 of sulphur). It is allowed to settle for half-an-hour, and then decanted through a filter. The precipitate is shaken up with boiling water, rendered slightly acid, filtered, washed, dried, ignited, and weighed. The ignited precipitate, when pure, is white, and is not decomposed at a red heat; it is barium sulphate (BaSO_{4}), and contains 13.73 per cent. of sulphur, or 34.33 per cent. of sulphuric oxide (SO_{3}).
~Determination of Sulphur in Pyrites.~--Weigh up half a gram of the dried and powdered sample, and treat with 10 c.c. of a mixture of 3 volumes of nitric acid and 1 volume of hydrochloric acid, occasionally heating. Evaporate to dryness, treat with 5 c.c. of hydrochloric acid, and again evaporate; take up with 1 c.c. of hydrochloric acid and 100 c.c. of hot water, filter through a small filter, and wash. The residue may contain sulphates of lead, barium, or lime; it must be separately examined, if the total sulphur is wanted. The filtrate is heated, and rendered slightly alkaline with ammonia. Filter off the precipitated ferric hydrate through a quick filter, and wash with hot water. If necessary, evaporate the bulk to about 200 c.c., render faintly acid with hydrochloric acid, and add 20 c.c. of solution of barium chloride; allow to stand for half-an-hour, and decant through a filter. Wash with hot water, dry, ignite, and weigh. Pure pyrites contains 53.33 per cent.
of sulphur.
VOLUMETRIC METHOD.
This is based upon the easy conversion of all sulphur compounds into sulphates by fusion with nitre or by oxidation with nitric acid; and on the determination of the sulphate formed by t.i.tration in an acetic acid solution with baric chloride.[101] The finishing point is determined by filtering off portions of the a.s.say solution, and testing with sulphuric acid. A slight excess of baric chloride will cause a precipitate.
The process may be divided into--(1) the preparation of the solution, and (2) the t.i.tration.
~Preparation of the Solution.~--Weigh up from 1 to 5 grams of the dried and powdered substance, and mix intimately with 4 grams of powdered nitre; clean out the mortar with another gram of nitre, and add this as a cover. Heat in a platinum crucible for fifteen minutes at a low temperature; cool, and extract with water in an evaporating-dish about 9 inches across, and holding 700 or 800 c.c. Add 10 grams of sodium acetate and 10 c.c. of acetic acid, and dilute to half a litre. Boil.
The solution is ready for t.i.trating. Substances which lose sulphur on heating (such as pyrites) are thus treated:--Weigh up 1 gram, and evaporate nearly to dryness with 10 c.c. each of nitric and hydrochloric acids. Take up with 10 c.c. of hydrochloric acid, and again boil down to a small bulk; dilute and transfer to a 9-inch evaporating-dish; add 10 grams of sodium acetate and 5 c.c. of acetic acid, dilute to half a litre, and boil. The solution is ready for t.i.trating. Sulphates may be dissolved up in the dish itself with the help of a c.c. or so of hydrochloric acid; sodium acetate and acetic acid are then added; and, after dilution and boiling, the solutions are at once t.i.trated.
The solution before t.i.tration must contain no free mineral acid, but 5 or 10 c.c. of acetic acid should be present. It must contain 10 grams of sodium acetate, or sufficient to convert any free mineral acid into its corresponding sodic salt; or, if chlorides, nitrates or sulphates of the metals are present, sufficient to decompose them. If a precipitation occurs, as is the case with ferric salts, &c., the solution is t.i.trated with the precipitate in it.
~The t.i.tration.~--_The standard solution of barium chloride_ is made by dissolving 76.25 grams of the crystallized salt (BaCl_{2}.2H_{2}O) in distilled water, and diluting to 1 litre. 100 c.c. will equal 1 gram of sulphur. As indicator, use dilute sulphuric acid. The strength of the solution may be checked by the t.i.tration of 5 grams of ferrous sulphate (oxidized with permanganate of pota.s.sium or a few drops of nitric acid), which should require 57.5 c.c. of the barium chloride solution; or any pure sulphate of known composition can be used; anhydrous salts should be preferred.