SILICON, CARBON, BORON.
SILICON AND SILICATES.
In assaying, more especially products direct from the mine, there is always found, when the rock is siliceous, a quantity of white sandy-looking substance, insoluble in acids, which is sometimes accompanied by a light gelatinous material very difficult to filter. This is variously described as "insoluble," "sand," "insoluble silicates," "gangue," or "rocky matter." It may be pure quartz; but oftener it is mixed with silicates from the rock containing the mineral. Some silicates, but not many, are completely decomposed by boiling with hydrochloric acid or aqua regia; and others are partly so, they yield a gelatinous precipitate of silica which greatly interferes with the filtering. It is a common practice with assayers to carry the first attack of the sample with acids to dryness, and to take up with a fresh portion of acid. By this means the separated silica becomes granular and insoluble, and capable of being filtered off and washed with comparative ease.
This residue may be ignited and weighed; and be reported as so much per cent. of "silica and silicates insoluble in acids." Unless specially wanted, a determination of its constituents need not be made. When required, the analysis is best made on the ignited residue, and separately reported as "analysis of the insoluble portion."
Silicon only occurs in nature in the oxidised state; but the oxide generally known as silica (SiO2) is common, being represented by the abundant minerals—quartz, flint, &c. Silica, combined with alumina, lime, oxide of iron, magnesia and the alkalies, forms a large number of rock-forming minerals. Most rock masses, other than limestones, contain over 50 per cent. of silica. The following are analyses of some of the commoner silicates; but it must be noted that these minerals often show great variation in composition. This is more especially true of chlorite, schorl, hornblende and augite.
| Silica, SiO2. | Alumina, Al2O3. | Ferric Oxide, Fe2O3. | Ferrous Oxide, FeO. | Lime, CaO. | Magnesia, MgO. | Potash, K2O. | Soda, Na2O. | Fluorine, Water &c. | |
| Potash-felspar | 65.2 | 18.2 | 0.2 | — | — | — | 14.7 | 1.5 | |
| Soda-felspar | 67.0 | 19.2 | — | 0.3 | 1.2 | 1.8 | 2.2 | 7.2 | |
| Lime-felspar | 43.3 | 35.4 | — | 1.3 | 17.4 | 0.35 | 0.5 | 0.9 | |
| Potash-mica | 45.7 | 33.7 | 3.1 | — | — | 1.1 | 7.5 | 2.8 | F (0.8) H2O (4.9) |
| Magnesia-mica | 39.1 | 15.4 | 7.1 | — | — | 23.6 | 7.5 | 2.6 | F (0.7) |
| Hornblende | 40.6 | 14.3 | 5.8 | 7.2 | 12.5 | 14.0 | 1.5 | 1.6 | |
| Augite | 50.0 | 3.7 | 2.4 | 6.6 | 22.8 | 13.5 | — | — | MnO (0.1) |
| Almandine (Garnet) | 39.7 | 19.7 | — | 39.7 | — | — | — | — | MnO (1.8) |
| Chlorite (Peach) | 32.1 | 18.5 | — | — | — | 36.7 | — | — | H2O (12.1) |
| Schorl | 37.0 | 33.1 | 9.3 | 6.2 | 0.5 | 2.6 | 0.7 | 1.4 | B2O3 (7.7) F (1.5) |
| China-clay | 46.7 | 39.6 | — | — | — | — | — | — | H2O (13.4) |
| Talc | 61.7 | — | — | 1.7 | — | 31.7 | — | — | H2O (3.8) |
| Serpentine | 42.9 | — | — | 3.8 | — | 40.5 | — | — | H2O (12.6) |
| Olivine | 39.3 | — | — | 14.8 | — | 45.8 | — | — |
Silicon, from a chemical point of view, is an interesting body. It combines with iron to form a silicide; and is present in this condition in cast iron. Only in the case of the analysis of this and similar substances is the assayer called on to report the percentage of silicon. Silicon is readily converted into silica by the action of oxidizing agents. Silica forms only one series of salts—the silicates—which have in many cases a complex constitution; thus there are a large number of double silicates, which vary among themselves, not only in the relation of base to acid (which is the essential difference), but also in the ratio of the bases between themselves (which varies with almost every specimen).
Silica is detected by heating the substance with a fluoride and sulphuric acid in a platinum-crucible. On holding a rod, moistened with a drop of water, over the escaping fumes, the white crust of silica formed on the drop of water shows its presence. The insolubility of a fragment of the mineral in a bead of microcosmic salt, is also a very good test; the fragment, on prolonged heating, does not lose its angular form.
There is no dry assay for this substance, nor volumetric method; when the determination is required, it is carried out gravimetrically and, generally, by the following plan.
If the sample contains oxides, sulphides, &c., in any quantity, these are first dissolved out by treatment with acid, evaporated to dryness, taken up with hydrochloric acid, and filtered. The dried residue is treated in the same way as the silicates. Some silicates are completely decomposed by such treatment; but it saves time (unless one is sure that no undecomposable silicate is present) to treat these in the same way as the others. On the other hand, there are some silicates which are only attacked with difficulty even by fusion with alkaline carbonates; consequently, it is always well to have the substance reduced to the finest state of division by careful powdering, as this greatly assists the subsequent action. With very hard silicates, the grinding away of the mortar in this operation will be perceptible; the foreign matter thus introduced must not be ignored. Previously igniting the substance sometimes assists the powdering; but it is best to use a steel mortar. The particles of steel can be removed by a magnet, or, where the nature of the substance will allow it, by boiling with a little dilute hydrochloric acid.
The dried and powdered material is intimately mixed with four times its weight of "fusion mixture" in a platinum-crucible or dish. It is then moderately heated over a Bunsen burner, and afterwards more strongly fused over a blast, or enclosed in a clay crucible in the wind-furnace. The action is continued until the fused mass is perfectly tranquil. With very refractory substances, the action must be long continued at a high temperature. When sufficiently cold, the crucible is examined to see that no particles of foreign matter are adhering to its outer surface. It is then transferred to a five- or six-inch evaporating-dish, where its contents are acted upon with warm water for some time. The "melt" will slowly dissolve, but the solution should be hastened by keeping the liquid moderately acid with hydrochloric acid. When the "melt" has dissolved, clean and remove the platinum-dish, and evaporate the solution to a paste. Continue the evaporation to dryness on a water-bath (not on the hot plate), and whilst drying stir with a glass rod, feeling at the bottom of the dish for any unfused particles, which, if present, can be detected by their grittiness. If there is much grit, it will be necessary to repeat the assay; but with a small quantity it will only be necessary to refuse the grit and silica after ignition.
During solution of the "melt" and evaporation (which may be carried on together), a clear solution will not be obtained, a flocculent silica will separate out, and towards the end of the evaporation the mass will get gelatinous. The drying of the jelly must be finished on the water-bath; first, because at this temperature the silica is rendered insoluble in hydrochloric acid, whilst the solubility of the alumina, iron, &c., is unaffected, which would not be the case at a much higher temperature; and second, because the gelatinous residue requires very cautious drying to prevent loss from spirting.
When dry, the substance is moistened, and heated with strong hydrochloric acid, and the sides of the dish are washed down with water. The silica is washed by decantation two or three times with hydrochloric acid and hot water, before being thrown on to the filter. The filtrate is again evaporated to dryness, taken up with a little hydrochloric acid and water and again filtered. The residue on the filter is silica. The two lots of silica are washed free from chlorides with hot water, dried on an air-bath, transferred to a platinum-crucible, ignited gently at first, at last strongly over the blast or in a muffle, cooled in a desiccator, and weighed.
The white powdery precipitate is silica (SiO2), and its weight, multiplied by 100, and divided by the weight of ore taken, gives the percentage of silica in the sample. Where the percentage of silicon is wanted, which is very rarely the case, it is got by multiplying this result by 0.4667. It is always necessary to examine the purity of the body weighed as silica. This is done by re-fusing the material weighed, and re-determining the silica in it; or, better, by mixing a weighed portion in a platinum-dish with a little strong sulphuric acid, covering with hydrofluoric acid, and evaporating. In the latter case, the silica will be converted into fluoride, which will be driven off, and the impurities will be left behind as sulphates of barium, phosphate and oxide of tin, titanium, &c. This must be weighed and deducted from the weight of the silica. In a complete examination of a silicate it should be treated with the precipitate containing alumina, ferric oxide, &c.
EXAMINATION OF SILICATES.
The student interested in the analysis of rocks and rock-forming minerals is advised to consult a valuable paper by Dr. W.F. Hillebrand in the Bulletin of the United States Geological Survey, No. 148, to which I am very largely indebted in the revision of the following pages.
Moisture.—Five grams of the powdered sample is dried between watch-glasses in the water-oven for two hours, or till its weight is constant; and the loss is reported as water lost at 100° C. The rest of the determinations are made on this dried mineral.
Combined Water, &c.—Weigh up 1 gram of the substance, and ignite over the blowpipe for some time in a platinum-crucible, cool in a desiccator, and weigh. Record the loss as "loss on ignition," not as "combined water."
Silica.—The ignition should have been performed in an oxidising atmosphere in a muffle or over a slanting blowpipe flame; this will ensure the oxidation of any pyrites or other sulphide present, which if unoxidised would injure the crucible in the next operation. The ignited residue is mixed with 6 or 7 grams of anhydrous sodium carbonate. This reagent should be the purest obtainable, but its purity should be checked, or rather its impurities should be determined by running a "check" or "blank" assay with 10 grams of it through the stages of the analysis; the impurities will be chiefly silica, alumina and lime, and altogether they ought not to exceed 1 milligram. The crucible with the mixture is heated at first gently over a Bunsen and afterwards more strongly in an oxidising atmosphere in a muffle or over the blowpipe. The fused mass is allowed to cool in the crucible, and is then dissolved out in a basin with water and a small excess of hydrochloric acid. After the removal and cleaning of the crucible, the liquor is evaporated almost to dryness. Dr. Hillebrand advises stopping short of complete dryness. The residue is taken up with a little hydrochloric acid and water and filtered and washed. The liquor, including the washings, is again evaporated and taken up with water and a little acid. Usually about 1 per cent. of silica will be thus recovered. It is to be filtered off and washed and added to the main silica. The filtrate is reserved. The silica, thoroughly washed, is dried and ignited at a high temperature for twenty or thirty minutes. It is then weighed in a platinum crucible. After weighing it is treated with hydrofluoric acid and a little sulphuric, carefully evaporated and ignited strongly. The residue, which in extreme cases may amount to 2 or 3 per cent. of the rock, is weighed and deducted from the weight of the impure silica. It is retained in the crucible.
Alumina, &c.—The filtrate from silica is treated by the basic acetate method. That is, it is first treated by a cautious addition of a solution of soda, almost to the point of producing a precipitate, in order to neutralise the excess of acid; 2 or 3 grams of sodium acetate are added, and the whole boiled for a minute or so. The precipitate is filtered off and washed only slightly. Save the filtrate. The precipitate is dissolved in hydrochloric, or, perhaps better, in nitric acid; and is reprecipitated by adding an excess of ammonia and boiling. The precipitate is filtered and washed with water containing 2 per cent. of ammonium nitrate. Both filtrates are evaporated separately to a small bulk, a drop or two of ammonia being added to the second towards the finish. They are next filtered into a 6 or 8-ounce flask through a small filter, the second filtrate coming after, and serving in a manner as wash water for the first[113]. The two washed alumina precipitates are dried and placed in the platinum crucible containing the residue from silica after treatment with hydrofluoric acid. They are then ignited in an oxidising atmosphere at a high temperature for about 10 minutes. The weight, including that of the residue from the silica, is noted as that of "alumina, &c."
The weighed oxides are next fused with bisulphate of potash for some hours. The bisulphate should have been first fused, apart, until the effervescence from the escape of steam has stopped. The melt is dissolved out with cold water and dilute sulphuric acid, and any insoluble residue is filtered off, washed, ignited and weighed. The filtrate is reserved for determinations of iron and titanium. The residue, after weighing, may be treated with hydrofluoric and sulphuric acids for any silica,[114] which would be determined by loss. It may be tested for barium sulphate by treatment with hot strong sulphuric acid; in which this salt dissolves, but is again insoluble (and so comes out as a white precipitate) on diluting with cold water; the acid also must be cold before adding the water. The filtrate containing the iron is reduced with sulphuretted hydrogen, boiled till free from that gas, filtered and titrated with a standard solution of permanganate of potassium. The iron found is calculated to ferric oxide by dividing by .7. The iron solution after titration serves for the determination of titanium oxide (TiO2). This is done colorimetrically, by adding peroxide of hydrogen free from hydrofluoric acid, and comparing the brown colour produced with that produced by the addition of a standard solution of titanium to an equal volume of water containing sulphuric acid.[115] The alumina is determined by difference. From the weight of the combined precipitate which has been recorded as "Alumina, &c.," deduct (1) the residue, insoluble, after fusion with bisulphate; (2) the ferric oxide; (3) the titanium oxide; and (4) the phosphoric oxide (P2O5), the amount of which is subsequently determined in a separate portion. This gives the alumina.
Manganous oxide, &c.—The filtrate from the "alumina, &c." contained in a 6 or 8-ounce flask, which it nearly fills, is made slightly alkaline with ammonia and treated with a small excess of ammonium sulphide; the flask is then corked and placed on one side for some time (a day or so) so that the manganese sulphide may separate. The precipitate is filtered off and washed with water containing ammonium chloride and a few drops of ammonium sulphide. The filtrate is reserved for lime, &c. The precipitate is digested with sulphuretted hydrogen water, to which one-fifth of its volume of strong hydrochloric acid has been added; this dissolves the sulphides of zinc and manganese; any black residue should be tested for copper and perhaps nickel. The solution is evaporated to dryness, taken up with a little water and treated with a small excess of solution of carbonate of soda. It is boiled and again evaporated, washed out with hot water and filtered on to a small filter, dried, ignited, and weighed as Mn3O4. It is calculated to MnO. It may contain, and should be tested for oxide of zinc, which, if present, must be deducted. If the dish becomes stained during evaporation, take up with a few drops of hydrochloric and sulphurous acids, evaporate, and then treat with carbonate of soda.
Lime, &c.—The filtrate from the manganese sulphide is boiled, and without cooling, treated with ammonium oxalate in solution, which also should be heated to boiling. The liquid is filtered off and reserved for magnesia. The precipitate is dissolved in very little hydrochloric acid and reprecipitated by adding ammonium oxalate and ammonia to the boiling solution. The filtrate and washings from this are reserved for magnesia. The precipitate is either dissolved in dilute sulphuric and titrated with permanganate of potash as described under Lime (p. 322); or it is ignited and weighed as oxide. In this last case it may be examined for barium and strontium, the former of which will rarely be present.
Magnesia.—The filtrate from the first lime precipitate is treated with sodium phosphate and ammonia, and allowed to stand overnight. It is then filtered. The precipitate is dissolved in hydrochloric acid; the solution is filtered into the beaker containing the solution from the second lime precipitate. Ammonia and sodium phosphate are again added, and the precipitate, after standing, is filtered off, washed with water containing ammonia; it is then dried, ignited and weighed as magnesium pyrophosphate. This is calculated into magnesia.
Potash and Soda.—Weigh out .5 gram of the dried ore, and mix with an equal quantity of ammonic chloride; and to the mixture add gradually 4 grams of calcium carbonate ("precipitated"). Introduce into a platinum-crucible and cover loosely. Heat, at first, gently; and then at a red heat for from forty to sixty minutes. Transfer to a porcelain dish, and digest with 60 or 80 c.c. of water; warm and filter: to the filtrate add ammonic carbonate and ammonia, and filter; evaporate the filtrate to dryness, adding a few drops more of ammonic carbonate towards the end; when dry, heat gently, and then raise the temperature to a little below redness. Dissolve in a small quantity of water, add a drop of ammonic carbonate, and filter through a small filter into a weighed platinum dish. Evaporate, ignite gently, and weigh. The residue contains the soda and potash of the mineral as chlorides.
To determine the proportion of potassium, dissolve this residue in a little water, add platinum chloride in excess, evaporate to a paste, extract with alcohol, decant through a small weighed filter, wash with alcohol, and dry at 100° C. Weigh. The substance is potassium platinic chloride (2KCl.PtCl4). Its weight, multiplied by 0.1941, will give the weight of potash (K2O).
To find the proportion of soda, multiply the weight of the potassium platinic chloride by 0.306; this gives the weight of potassium chloride. Deduct this from the weight of the mixed chlorides first got; the difference will be the sodium chloride, which weight, multiplied by 0.53, will give the weight of soda (Na2O).
Ferrous Oxide.—When a qualitative test shows both ferric and ferrous oxide to be present, the proportion of the ferrous oxide must be separately determined. The finely ground mineral mixed with dilute sulphuric acid is treated on a water bath with hydrofluoric acid. Solution is best effected in an atmosphere of carbonic acid. In about an hour the decomposition is complete, and the solution is diluted with cold water, and titrated with the solution of bichromate or of permanganate of potassium. The iron found is multiplied by 1.286, and reported as ferrous oxide. To find the proportion of ferric oxide, the ferrous iron found is multiplied by 1.428, and this is deducted from the weight of ferric oxide obtained by precipitation with ammonia. The ammonia precipitate contains the whole of the iron as ferric oxide; hence the necessity for calculating the ferrous oxide as ferric, and deducting it.
Phosphoric Oxide (P2O5).—Weigh up 5 grams of the finely-divided and dry sample, and digest with 10 or 20 c.c. of nitric acid; evaporate to dryness on the water-bath; take up with a little dilute nitric acid; dilute with water; and filter. Add a few grams of ammonic nitrate and 10 c.c. of ammonium molybdate solution, heat nearly to boiling, and allow to settle; filter off, and wash the yellow precipitate. Dissolve with dilute ammonia, add "magnesia mixture," and allow to stand overnight. Filter, wash with dilute ammonia, dry, ignite, and weigh as pyrophosphate of magnesia. The weight, multiplied by 0.6396, gives the weight of phosphoric oxide.
Soluble Silica.—Some silicates are acted on by hydrochloric acid, and leave on evaporation a residue; which, when the soluble salts have been washed out, consists generally of the separated silica with perhaps quartz and unattacked silicates. It should be ignited, weighed and boiled with a solution containing less than 10 per cent. of caustic soda: this dissolves the separated silica. The liquor is diluted, rendered faintly acid, and filtered. The residue is washed, ignited and weighed. The loss gives the soluble silica.
Estimation of Silica in Slags (Ferrous silicates).—Take 1 gram of the powdered slag, treat with aqua regia, evaporate to dryness, extract with hydrochloric acid, filter, dry, ignite, and fuse the ignited residue with "fusion mixture," then separate and weigh the silica in the usual way. Slags are for the most part decomposed by boiling with aqua regia, but it will be found more convenient and accurate to first extract with acids and then to treat the residue as an insoluble silicate.
Estimation of "Silica and Insoluble Silicates" in an Ore.—Take 2 grams of the powdered mineral, evaporate with nitric acid (if sulphides are present), treat the dried residue (or the original substance if sulphides are absent) with 10 or 20 c.c. of hydrochloric acid; again evaporate to dryness, take up with dilute hydrochloric acid, filter, wash, ignite, and weigh.
Estimation of Silicon in Iron.—Place 2 grams of the metal (borings or filings) in a four-inch evaporating dish, and dissolve (with aid of heat) in 25 c.c. of dilute nitric acid. Evaporate to complete dryness, take up with 20 c.c. of hydrochloric acid, and allow to digest for one hour. Boil down to a small bulk, dilute with a 5 per cent. solution of hydrochloric acid, boil, and filter. Wash with acid and water, dry, ignite in a platinum crucible, and weigh the SiO2. This, multiplied by 0.4673, gives the weight of the silicon. The percentage is calculated in the usual way.
PRACTICAL EXERCISES.
1. A certain rock is a mixture of 70 per cent. of quartz, 25 per cent. of potash-felspar, and 5 per cent. of potash-mica. What per cent. of silica will it contain?
2. Two grams of a mixture of silica and cassiterite left, after reduction in hydrogen, 1.78 grams. Assuming all the oxide of tin to have been reduced, what will be the percentage of silica?
3. The formula of a compound is 2FeO.SiO2. What percentage of silica will it contain?
4. Two grams of a sample of cast-iron gave 0.025 gram of silica. Find the percentage of silicon in the metal.
5. What weights of quartz and marble (CaCO3) would you take to make 30 grams of a slag having the formula CaO.SiO2?
CARBON AND CARBONATES.
Carbon compounds enter so largely into the structure of organised bodies that their chemistry is generally considered apart from that of the other elements under the head of Organic Chemistry. Carbon occurs, however, among minerals not only in the oxidised state (as carbonates), but also in the elementary form (as in diamond and graphite), and combined with hydrogen, oxygen, &c. (as in petroleums, bitumens, lignites, shales, and coals). In small quantities "organic matter" is widely diffused in minerals and rocks. In shales and clays it may amount to as much as 10 or 20 per cent. (mainly as bituminous and coaly matters).
The assayer has only to take account of the organic matter when it is of commercial importance, so that in assays it is generally included under "loss on ignition."
In coals, shales, lignites, &c., the carbon compounds are, on heating, split up into oils and similar compounds. The products of distillation may be classified as water, gas, tars, coke, and ash. The assay of these bodies generally resolves itself into a distillation, and, in the case of the shales, an examination of the distillates for the useful oils, paraffin, creosote, &c., contained in them.
Elementary carbon is found in nature in three different forms, but these all re-act chemically in the same way. They combine with oxygen to form the dioxide.[116] The weight of oxygen required to burn a given weight of any form of carbon is the same, and the resulting product from all three has the same characteristic properties. Carbon dioxide is the common oxide of carbon. A lower oxide exists, but on burning it is converted into the dioxide. Wherever the oxidation of carbon takes place, if there is sufficient oxygen, carbon dioxide (carbonic acid) is formed; this re-action is the one used for the determination of carbon in bodies generally. The dioxide has acid properties, and combines with lime and other bases forming a series of salts called carbonates.
The carbon-compounds (other than carbonates, which will be subsequently considered) occurring in minerals are generally characterised by their sparing solubility in acids. The diamond is distinguished from other crystals by its hardness, lustre, and specific gravity. It may be subjected to a red heat without being apparently affected, but at a higher temperature it slowly burns away. Graphite, also, burns slowly, but at a lower temperature. The other bodies (coals, shales, &c.) differ considerably among themselves in the temperature at which they commence to burn. Some, such as anthracite, burn with little or no flame, but most give off gases, which burn with a luminous flame. They deflagrate when sprinkled on fused nitre, forming carbonate of potash. In making this test the student must remember that sulphur and, in fact, all oxidisable bodies similarly deflagrate, but it is only in the case of carbon compounds that carbonate of potash is formed. Carbon unites with iron and some of the metals to form carbides; combined carbon of this kind is detected by the odour of the carburetted hydrogen evolved when the metal is treated with hydrochloric acid; for example, on dissolving steel in acid.
The natural carbon compounds, although, speaking generally, insoluble in hydrochloric or nitric acids, are more or less attacked by aqua regia. The assayer seldom requires these compounds to be in solution. The presence of "organic matter"[117] interferes with most of the reactions which are used for the determination of the metals. Consequently, in such cases, it should be removed by calcination unless it is known that its presence will not interfere. When calcination is not admissible it may be destroyed by heating with strong sulphuric acid and bichromate or permanganate of potash or by fusion with nitre.
Carbon may be separated from other substances by conversion into carbon dioxide by burning. In most cases substances soluble in acids are first removed, and the insoluble residue dried, weighed, and then calcined or burned in a current of air. The quantity of "organic matter" may be determined indirectly by the loss the substance undergoes, but it is better to determine the "organic carbon" by confining the calcination in a tube, and collecting and weighing the carbon dioxide formed. Each gram of carbon dioxide is equivalent to 0.2727 gram of carbon.
Instead of a current of oxygen or air, oxide of copper may be more conveniently used. The operation is as follows:—Take a clean and dry piece of combustion tube drawn out and closed at one end, as shown in the figure (fig. 70), and about eighteen inches long. Fit it with a perforated cork connected with a U-tube (containing freshly-fused calcium chloride in coarse grains) and a set of potash bulbs (fig. 71) (containing a strong solution of potash), the exit of which last is provided with a small tube containing calcium chloride or a stick of potash. Both the U-tube and bulbs should have a loop of fine wire, by which they may be suspended on the hook of the balance for convenience in weighing. They must both be weighed before the combustion is commenced; to prevent absorption of moisture during weighing, &c., the ends are plugged with pieces of tube and glass rod.
Fill the combustion tube to a depth of about eight inches with some copper oxide, which has been recently ignited and cooled in a close vessel. Put in the weighed portion for assay and a little fresh copper oxide, and mix in the tube by means of an iron wire shaped at the end after the manner of a corkscrew. Put in some more oxide of copper, and clean the stirrer in it. Close loosely with a plug of recently ignited asbestos, place in the furnace, and connect the U-tube and bulbs in the way shown in the sketch (fig. 72).
See that the joints are tight, and then commence the combustion by lighting the burners nearest the U-tube; make the first three or four inches red hot, and gradually extend the heat backwards the length of the tube, but avoid too rapid a disengagement of gas. When gas ceases to come off, open the pointed end of the tube and draw a current of dried air through the apparatus.
The carbon dioxide is absorbed in the potash bulbs, and their increase in weight multiplied 0.2727 gives the amount of carbon in the substance taken.
The increase in weight in the calcium chloride tube will be due to the water formed by the oxidation of the combined hydrogen. If this last is required the increase in weight multiplied by 0.111 gives its amount.
COALS.
The determination of the actual carbon in coals and shales is seldom called for; if required, it would be performed in the way just described.[118] The ordinary assay of a sample of coal involves the following determinations—moisture, volatile matter, fixed carbon, ash, and sulphur. These are thus carried out:—
Determination of Moisture.—Take 3 grams of the powdered sample and dry in a water-bath for an hour or so. The loss is reported as moisture. Coals carry from 1 to 2 per cent. If the drying is carried too far, coals gain a little in weight owing to oxidation, so that it is not advisable to extend it over more than one or two hours.
Determination of Volatile Matter.—This determination is an approximate one, and it is only when working under the same conditions with regard to time, amount of coal taken, and degree of heat used, that concordant results can be arrived at. It is a matter of importance whether the coal has been previously dried before heating or not, since a difference of 2 per cent. may be got by working on the dried or undried sample. Take 2 grams of the powdered, but undried, sample of coal, place in a weighed platinum crucible, and support this over a good Bunsen burner by means of a thin platinum-wire triangle. The heat is continued until no further quantity of gas comes off and burns at the mouth. This takes only a few minutes. The cover is tightly fitted on, and when cold the crucible is weighed. The loss in weight, after deducting the moisture, gives the "volatile matter," and the residue consists of "fixed carbon" and "ash."
Determination of Ash.—The coke produced in the last operation is turned out into a porcelain dish and ignited over a Bunsen burner till the residue is free from particles of carbon. Calcination is hastened by stirring with a platinum wire. The operation may be done in a muffle, but this gives results a few tenths of a per cent. too low. The dish is cooled in a dessicator, and weighed. The increase in weight gives the amount of "ash," and the difference between this and the weight of the coke gives the "fixed carbon."
The assay is reported as follows:—
| Moisture at 100° C. | __ | per cent. |
| Volatile matter | __ | " |
| Fixed carbon | __ | " |
| Ash | __ | " |
| contains sulphur __ per cent. |
Determination of Sulphur.—The sulphur exists in the coal partly in organic combination, partly as metallic sulphide (iron pyrites, marcasite, &c.), and, perhaps, as sulphate. So that the sulphur determination must be separately reported, since a portion will go off with the volatile matter, and the remainder would be retained and weighed with the coke.
The sulphur is thus determined:—Take 1 gram of the coal and mix with 1.5 gram of a mixture of 2 parts of calcined magnesia and 1 part of carbonate of soda, and heat in a platinum crucible for one hour or until oxidation is complete. Turn out the mass and extract it with water and bromine, filter, acidulate with hydrochloric acid, boil off the bromine, and precipitate with baric chloride (estimating gravimetrically as given under Sulphur). Another method is as follows:—Take 1 gram of the coal and drop it gradually from a sheet of note paper on to 5 grams of fused nitre contained in a platinum dish. Extract with water, acidify with acetic acid, and estimate volumetrically as described under Sulphur.
Calorific Effect of Coals.—The heat-giving value of a coal is best expressed in the number of pounds of water, previously heated to the boiling point, which it will convert into steam. This is generally termed its evaporative-power. It may be determined by means of the calorimeter (fig. 73). This consists of a glass cylinder marked to hold 29.010 grains of water. The instrument consists of a perforated copper stand, provided with a socket and three springs. The socket holds a copper cylinder which is charged with 30 grains of the dried coal mixed with 300 grains of a mixture of 3 parts of potassium chlorate and 1 part of nitre. The charge is well packed in the cylinder and provided with a small fuse of cotton saturated with nitre. Fill the glass cylinder to its mark with water and take the temperature with a thermometer marked in degrees Fahrenheit. Ignite the fuse and immediately cover with the outer copper cylinder (extinguisher-fashion), which will be held in its place by the springs. The stop-cock should be closed before this is done. Place the apparatus quickly in the cylinder of water. When the action is over open the stop-cock and agitate the water by raising and lowering the instrument a few times. Again take the temperature. The rise in temperature, plus 10 per cent. for the heat used in warming the apparatus and lost by radiation, gives the evaporative-power.
The following is an example:—
| Temperature before experiment | 67.0° | F. |
| Temperature after " | 79.0° | " |
| ———— | ||
| Rise | 12.0° | " |
| + 1/10th | 1.2° | " |
| ———— | ||
| Gives | 13.2° | " |
One pound of the coal will evaporate 13.2 pounds of water.
SHALES, ETC.
The assay of these is carried out in the same way as that of coals, but the volatile matters are separately examined, and, in consequence, a larger quantity of material must be used. For the moisture, volatile matter, fixed carbon and ash, the determinations are the same, but a special distillation must be made to obtain a sufficient quantity of the volatile products for subsequent examination. Take 500 or 1000 grams of the well-sampled and powdered shale, and introduce into a cast-iron retort as shown in fig. 74. Lute the joint with fire-clay, place the cover on, and bolt it down. The bolts should have a covering of fire-clay to protect them from the action of the fire. Place the retort in a wind furnace, supporting it on a brick, and pack well around with coke. Build up the furnace around and over the retort with loose fire-bricks, and heat gradually.
As soon as water begins to drip, the tube of the retort is cooled by wrapping a wet cloth around it, and keeping wet with water. The water is kept from running into the receiver by a ring of damp fire-clay. A quantity of gas first comes over and will be lost, afterwards water and oily matters. The retort must be red hot at the close of the distillation, and when nothing more distils off, which occurs in about two or three hours, the wet cloth is removed, and the tube heated with a Bunsen burner to drive forward the matter condensed in it into the receiver, and thus to clean the tube. It can be seen when the tube is clean by looking up through it into the red-hot retort. The receiver is then removed, and the retort, taken from the furnace, is allowed to cool. When cold it is opened, and the fixed carbon and ash weighed, as a check on the smaller assay.
The distillate of water and oil is warmed, and will separate into two layers, the upper one of which is oil, and the lower water. These are measured, and if the specific gravity of the oil is taken, its weight may be calculated. If the two liquids do not separate well, the water may be filtered off, after cooling, through a damped filter. The separation is, however, best effected in a separator (fig. 75). The liquids are poured into this, allowed to settle, and the lower layer drained off. The volume of the water is measured and its weight calculated in per cents. on the amount of shale taken.
Examination of the Oil.—A sufficient quantity of the oil must be got, so that if one distillation does not yield enough, the requisite quantity must be obtained by making two or more distillations. The oils are mixed, and the mixture, after having had its volume and specific gravity ascertained, is placed in a copper retort, and re-distilled with the aid of a current of steam. The residue in the retort is coke.
The distillate is separated from the water by means of the separator, and shaken for ten minutes with one-twentieth of its bulk of sulphuric acid (sp. g. 1.70). The temperature should not be allowed to rise above 40°. Allow to stand, and run off the "acid tar."
The oil is now shaken up with from 10 c.c. to 20 c.c. of sodic hydrate solution (sp. g. 1.3), allowed to stand, warmed for half-an-hour, and the "soda-tar" run off.
On mixing this soda-tar with dilute acid, the "crude shale oil creosote" separates, and is measured off.
The purified oil is next re-distilled in fractions, which come over in the following order:—"Naphtha," "light oil," "heavy oil," and "still bottoms." For the first product, which is only got from certain shales, the receiver is changed when the distillate has a specific gravity of 0.78. For the second product the process is continued till a drop of the distillate, caught as it falls from the neck of the retort on a cold spatula, shows signs of solidifying. This is "crude light oil."
The receiver is changed, and the "heavy oil" comes over; towards the end a thick brown or yellow viscid product is got. The receiver is again changed, and the distillation carried to dryness.
The "crude light oil" is washed cold with 2 per cent. of sulphuric acid (concentrated), and afterwards with excess of soda. Thus purified it is again distilled to dryness, three fractions being collected as before. Naphtha, which is added to the main portion, and measured; "light oil," which is also measured; and "heavy oil," which is added to that got in the first distillation. This last is poured into a flat-bottom capsule, and allowed to cool slowly. The temperature may with advantage be carried below freezing-point. The cooled cake is pressed between folds of linen, and the paraffin scale detached and weighed.
The results may be reported thus:—
| Naphtha, sp. g. | —— |
| Light oil, sp. g. | —— |
| Heavy oil, sp. g. | —— |
| Paraffin scale | —— |
| Coke, &c. | —— |
The results are calculated in per cents. on the oil taken. Some workers take their fractions at each rise of 50° C. The composition of average shale, as given by Mills, is as follows:—Specific gravity, 1.877; moisture, 2.54.
| Gas | } | |
| Volatile matter, water, ammonia | } | 23.53 |
| Oil | } | |
| Fixed carbon | 12.69 | |
| Ash | 63.74 | |
| _____ | ||
| 99.96 |
The ash is made up of silica, 55.6; ferric oxide, 12.2; alumina, 22.14; lime, 1.5; sulphur, 0.9; soluble salts (containing 0.92 per cent. sulphuric oxide), 8.3.
| Total | sulphur | in shale | 1.8 | per cent. |
| " | " | in ash | 1.3 | " |
For further information on these assays, and for the assay of petroleums, bitumens, &c., the student is referred to Allen's "Commercial Organic Analysis," Vol. II.
Determination of Organic Carbon in a Limestone.—Take 1 or 2 grams and dissolve with a very slight excess of dilute hydrochloric acid, evaporate to dryness, and determine the carbon in the residue by combustion with copper oxide.
Estimation of Carbon in a Sample of Graphite (Black-lead).—Weigh up 1 or 2 grams in a dish and calcine in the muffle till the carbon is burnt off. Weigh the residue, and calculate the carbon by difference.
Determination of Carbon in Iron.—The carbon exists in two states—free (graphite) and combined. The following process estimates the total carbon:—The carbon existing as graphite may be separately estimated in another portion by the same process, but using hydrochloric acid to dissolve the iron instead of the copper solution:—Weigh up 2 grams of the iron (or a larger quantity if very poor in carbon), and attack it with 30 grams of ammonic-cupric chloride[119] dissolved in 100 c.c. of water. Let the reaction proceed for a quarter-of-an-hour, and then warm until the copper is dissolved. Allow to settle, and filter through a filtering-tube. This is a piece of combustion tube drawn out and narrowed at one end, as shown in fig. 76. The narrow part is blocked with a pea of baked clay, and on this is placed half-an-inch of silica sand (previously calcined to remove organic matter), then a small plug of asbestos, and then a quarter-of-an-inch of sand. The tube is connected with a pump working at a gentle pressure, and the solution is filtered through the tube with the aid of a small funnel (fig. 77). The residue is washed, first with dilute hydrochloric acid, and then with distilled water. The tube is dried by aspirating air through it, and gently warming with a Bunsen burner. The tube is then placed in a small combustion-furnace, and connected with calcium chloride and potash bulbs, as shown in fig. 78. The potash bulb to the right of the figure must be weighed. A slow stream of air is drawn through the apparatus, and the heat gradually raised; in from thirty minutes to one hour the combustion will be complete. The potash bulbs are then disconnected and weighed, and the increase multiplied by 0.2727 gives the weight of carbon.
CARBONATES.
Carbon dioxide, which is formed by the complete oxidation of carbon, is a gas with a sweetish odour and taste, having a strong affinity for alkalies, and forming a series of compounds termed carbonates. The gas itself occurs in nature, and is sometimes met with in quantity in mining. The carbonates occur largely in nature, forming mountain masses of limestone, &c. Carbonates of many of the metals, such as carbonate of lead (cerussite), carbonate of iron (chalybite), carbonates of copper (malachite and chessylite), and carbonate of magnesia (magnesite), are common.
All the carbonates (those of the alkalies and alkaline earths excepted) are completely decomposed on ignition into the oxide of the metal and carbon dioxide; but the temperature required for this decomposition varies with the nature of the base. All carbonates are soluble with effervescence in dilute acids; some, such as chalybite and magnesite, require the aid of heat. The alkaline carbonates are soluble in water; the rest, with the exception of the bicarbonates, are insoluble therein.
Carbonates are recognised by their effervescence with acids—a stream of bubbles of gas are given off which collect in the tube, and possess the property of extinguishing a lighted match. The most characteristic test for the gas is a white precipitate, which is produced by passing it into lime or baryta-water, or into a solution of subacetate of lead.
The expulsion of carbon dioxide by the stronger acids serves for the separation of this body from the other acids and bases.
Dry Assay.—There is no dry assay in use. Any method which may be adopted will necessarily be applicable only to special compounds.
WET METHODS.
There are several methods in use which leave little to be desired either in speed or accuracy. We will give (1) a gravimetric method in which the estimation may be made directly by weighing the carbonic acid, or, indirectly, by estimating the carbon dioxide from the loss; (2) a volumetric one, by which an indirect determination is made of the gas; and (3) a gasometric method, in which the volume of carbon dioxide given off is measured, and its weight deducted.
Direct Gravimetric Method.—Fit up the apparatus shown in the diagram (fig. 79). The various tubes are supported by a fixed rod with nails and wire loops, and connected by short lengths of rubber-tubing. The first tube contains soda-lime. The small flask is fitted with a rubber-stopper perforated with two holes, through one of which passes the tube of a pipette holding 25 or 30 c.c. This pipette is to contain the acid. The substance to be determined is weighed out into the flask. The second tube contains strong sulphuric acid; the third, pumice stone, saturated with copper sulphate solution, and dried until nearly white (at 200° C.); the fourth contains recently fused calcium chloride; and the fifth, which is the weighed tube in which the carbonic acid is absorbed, contains calcium chloride and soda-lime,[120] as shown in fig. 80. The sixth also contains calcium chloride and soda-lime; its object is to prevent the access of moisture and carbonic acid to the weighed tube from this direction; it is connected with an aspirator.
Having weighed the U-tube and got the apparatus in order, weigh up 1, 2, or 5 grams of the substance and place in the flask. Fill the pipette with dilute acid, close the clamp, and cork the flask. Then see that the apparatus is tight. Open the clamp and allow from 10 to 20 c.c. of the acid to run on to the assay. Carbonic acid will be evolved and will be driven through the tubes. The gas should bubble through the sulphuric acid in a moderate and regular stream. When the effervescence slackens the clamp is opened and the greater part of the remaining acid run in. When the effervescence has ceased the clamp is opened to its full extent and a current of air drawn through with an aspirator. A gentle heat is applied to the flask; but it should not be prolonged or carried to boiling. After the removal of the heat a gentle current of air is drawn through the apparatus for 30 or 40 minutes. The weighed U-tube, which in the early part of the operation will have become warm if much carbonic acid was present, will by this time be cold. It is disconnected, plugged, and weighed. The increase in weight is due to the carbon dioxide of the sample.
Example.—Ore taken 1 gram.
| Weight | of tube, | before | 42.6525 | grams |
| " | " | after | 43.0940 | " |
| ———- | ||||
| Increase | equals CO2 | 0.4415 | " |
Indirect Gravimetric, or Determination by Loss.—Take a Geissler's carbonic-acid apparatus (fig. 81) and place in the double bulb some strong sulphuric acid. Put into the other bulb, the stopcock being closed, 3 or 4 c.c. of nitric acid diluted with water. Leave the apparatus in the balance-box for a few minutes and weigh. Introduce into the flask (through A) about 1 gram of the powdered substance and again weigh to find the exact amount added. Allow the acid to run gradually on to the carbonate, and when solution is complete, heat and aspirate. Cool and again weigh; the loss in weight is the carbonic acid.
For Example:—
| Weight | of apparatus | and acids | 85.494 | grams |
| " | " | marble | 86.879 | " |
| ——— | ||||
| Equal | to marble taken | 1.385 | " | |
| Weight | of apparatus | and marble | 86.879 | grams |
| " | " | minus carbonic acid | 86.2692 | " |
| ——— | ||||
| Equal | to carbonic acid | 0.6098 | " |
1.385 : 100 :: 0.6098 : x
x = 44.03 per cent.
The substance contains 44.03 per cent. of carbonic acid; a duplicate experiment gave 43.73 per cent.
This method is quicker, but less exact, than the direct gravimetric determination.
VOLUMETRIC METHOD.
This, which is of somewhat limited application, is based upon the determination of the quantity of acid required to decompose the carbonate. It consists in adding to a weighed quantity of the mineral a known amount of standard solution of acid which is in excess of that required to effect the decomposition. The quantity of residual acid is then determined by titrating with standard solution of alkali. This method has been described under Lime.
GASOMETRIC METHOD.
This method is the quickest of all, and the least troublesome after the apparatus has been once prepared. It yields fairly accurate results when worked in the manner described below; but if greater precautions are taken the results are exact. It depends on the measurement of the volume of gas given off on treating the weighed sample with acid. The apparatus described, page 52, is used. Weigh out a portion of the mineral which shall contain not more than 0.15 gram of carbonic acid (or 0.4 gram of carbonate of lime) and put it in the bottle. Put in the inner tube 10 c.c. of dilute hydrochloric acid (1—1), cork tightly, and read off the level of the liquid in the burette after adjusting the pressure. Turn the acid over on to the mineral. Run out the water so as to keep the level in the two burettes the same. When effervescence has ceased, rotate the contents of the bottle; finally, adjust the level in the burettes and read off the volume. The increase in volume is due to the evolved carbon dioxide. At the same time read off the "volume corrector."
Some of the carbon dioxide remains dissolved in the acid in the generating bottle, and the quantity thus dissolved will depend on the amount of carbonate as well as on the amount of acid present. Consequently, a measured quantity of acid should be used in each assay and a comparative experiment made with a known weight of pure carbonate of lime which will yield about the same volume of gas. The number of c.c. of gas got in the assay multiplied by 4.7 will give the number of milligrams of pure carbonate of lime that must be taken for the standard. With ordinary work the error rarely exceeds half a c.c.
The following example will illustrate the calculations:—
One gram of a mineral was taken, and yielded 49.0 c.c. of gas. The "volume corrector" reading was 100.4 c.c.
0.2405 gram of pure carbonate of lime was then taken, and treated in the same way; 50.5 c.c. of gas were got. The volume corrector still read 100.4 c.c.
0.2405 gram of carbonate of lime is equivalent to 0.1058 gram of carbon dioxide; then,
| 50.5 : 49.0 :: 0.1058 : x |
| x = 10.26 per cent. |
Estimation of Carbonic Acid in the Air of Mines.—According to a series of analyses by Angus Smith, the proportion of carbonic acid in the air of underground workings varied from 0.04 to 2.7 per cent. by volume. In places where men are working the proportion ought not to reach 0.25 per cent.
A simple method of determining whether a sample of air reaches this limit (0.25 per cent.) is described by Dr. C. Le Neve Foster in the "Proceedings of the Mining Association and Institute of Cornwall" for 1888. The apparatus used is an ordinary corked 8-ounce medicine bottle. This is filled with the air to be examined by sucking out its contents with a piece of rubber-tube. Half-an-ounce of dilute lime-water[121] (tinted with phenolphthalein) is poured in. If, on corking the bottle and shaking, the colour is not discharged, the air contains less than 0.25 per cent. of carbon dioxide. "If the colour fades slowly, and does not finally vanish till after a great deal of shaking, it may be assumed that the percentage of carbon dioxide does not greatly exceed one quarter; whereas, if the disappearance is rapid after a very few shakes, the contrary, of course, is the case." The dilute lime-water is measured out and carried in ordinary half-ounce phials. This method does not pretend to great accuracy, but as a method of distinguishing between good and bad air it is very convenient, and will be found useful.
For determining the actual proportion in the air the following plan is adopted:—Take a bottle which will hold about 50 ounces, and measure its capacity; fill the bottle with the air to be examined, pour in 100 c.c. of lime-water, and shake up for some time; add phenolphthalein, and titrate the remaining calcium hydrate with standard solution of oxalic acid.
The solution of oxalic acid is made by dissolving 2.25 grams of re-crystallised oxalic acid (H2C2O4.2H2O) in water and diluting to 1 litre. One c.c. = 0.001 gram of lime (CaO), or 0.0007857 gram of carbon dioxide.
Take 100 c.c. of the same lime-water, to which add the same amount of phenolphthalein as before. Titrate. The difference between the two readings gives the amount of "acid" equivalent to the lime-water neutralised by the carbon dioxide. The number of c.c. thus used up, when multiplied by 0.3989, gives the number of c.c. of carbon dioxide (at 0° C. and 760 mm.) in the volume of air taken. This volume, which is that of the bottle less 100 c.c., must in accurate work be reduced to the normal temperature and pressure.[122] The percentage by volume can then be calculated.
PRACTICAL EXERCISES.
1. In a gasometric determination 71.3 c.c. of gas were obtained from 0.2055 gram of mineral. The "volume corrector" reading was 102.2 c.c. 0.3445 gram of pure carbonate of lime gave 74.1 c.c. The "volume corrector" reading was 100.6. What is the percentage of carbon dioxide in the substance?
2. What volume of dry gas at 0° C. and 760 m.m. pressure should be obtained from 0.3445 gram of carbonate of lime? 1 c.c. of CO2 under these conditions weighs 1.97 milligrams.
3. A sample of coal is reported on as follows:—
| Specific gravity | 1.315 |
| Moisture | 1.001 |
| Volatile matter | 35.484 |
| Fixed carbon | 50.172 |
| Ash | 12.028 |
| ——— | |
| 100.000 |
What is there about this requiring explanation?
4. Calculate the percentage of carbonic acid in a mineral from the following data:—
| Weight | of apparatus | and acids | 87.0888 | grams | |
| " | " | " | plus mineral | 88.8858 | " |
| " | " | " | after loss of carbonic acid | 88.1000 | " |
5. A sample of pig iron contains 1.43 per cent. of "combined" and 2.02 per cent. of "free" carbon. Taking 2 grams of it for each determination, what weight of CO2 will be got on burning the residue from solution in ammonium cupric chloride, and what from the residue after solution in hydrochloric acid?
BORON AND BORATES.
Boron occurs in nature as boric acid or sassoline (H3BO3); borax or tincal (Na2B4O7.10H2O); ulexite or boronatrocalcite (2CaB4O7.Na2B4O7); borocalcite (CaB4O7.4H2O); boracite, 2Mg3B8O15.MgCl2, and some other minerals. Boric acid is also a constituent of certain silicates, such as tourmaline, axinite, and datholite.
The natural borates are used in the preparation of borax, which is largely employed as a preservative agent, for fluxing, and for other purposes.
There is only one series of boron compounds which have any importance. These are the borates in which the trioxide (B2O3) acts the part of a weak acid. The addition of any acid liberates boric acid, which separates out in cold solutions as a crystalline precipitate. Boric acid is soluble in alcohol and in hot water. On evaporating these solutions it is volatilised, although the anhydrous oxide is "fixed" at a red heat. The borates are mostly fusible compounds, and are soluble in acids and in solutions of ammonic salts.
Detection.—Boron in small quantities will escape detection unless specially looked for, but there is no difficulty in detecting its presence. Heated in the Bunsen-burner flame with "Turner's test," it gives an evanescent yellowish-green colour, due to fluoride of boron (BF3). "Turner's test" is a mixture of 5 parts of bisulphate of potash and 1 part of fluor spar. Boric acid itself imparts a characteristic green colour to the flame, which gives a spectrum made up of four well-marked and equidistant lines, three in the green and one in the blue. Solutions of boric acid give with "turmeric paper," which has been dipped into it and dried, a characteristic red tint. This is a very delicate test, but in trying it a blank experiment should be carried out alongside with a solution made up of the same re-agents which have been used in liberating the boric acid in the sample.
Solution and Separation.—The solution presents no difficulty, but the separation is troublesome. The best method is that of Gooch; who, if necessary, first fuses with carbonate of soda, and after the removal of chlorides and fluorides (by nitrate of silver or a lime salt), evaporates the aqueous extract with nitric or acetic acid to dryness in a retort and, subsequently, with repeated doses of 10 c.c. each of methyl alcohol. The distillate contains the boron as boric acid. Half a gram of the trioxide (B2O3) is completely carried over by two evaporations, each with 10 c.c. of the alcohol; but if water or foreign salts are present, more than this is required. In ordinary cases six such evaporations are sufficient for 0.2 gram of the oxide.[123]
GRAVIMETRIC DETERMINATION.
Before the introduction of Gooch's process it was usual to determine the boron trioxide "by difference." If the alcoholic distillate containing the boric acid is digested with about 1 gram (a known weight) of lime for ten or fifteen minutes, the alcohol can be evaporated off without danger of loss. Either calcium nitrate or acetate (which will be formed at the same time) yields lime upon subsequent ignition. Consequently, the increase in weight, after ignition, upon that of the lime taken gives the amount of boron trioxide present. The trioxide contains 31.4 per cent. of boron (B). Since magnesia does not form a soluble hydrate it cannot satisfactorily be used instead of lime.
The apparatus required is shown in fig. 82. It consists of a small retort or evaporating vessel made out of a pipette of 200 c.c. capacity. This is heated by means of a paraffin-bath at 130° or 140° C. It is connected with an upright condenser, at the lower end of which is a small flask which serves as a receiver.
The quantity of the borate taken should contain not more than 0.2 gram of the trioxide. Insoluble compounds are "dissolved in nitric acid at once, or, if necessary, first fused with sodium carbonate." With soluble and alkaline borates sufficient nitric acid is added to render it faintly acid. The solution is then introduced into the retort.
"The lime, to retain the boric acid in the distillate, is ignited in the crucible in which the evaporation of the distillate is to be made subsequently." It is then cooled in the desiccator for ten minutes, and weighed. The lime is transferred to the receiving flask and slaked with a little water. The retort is lowered into the bath so that "only the rear dips below the surface." The evaporation is carried to dryness, the retort being lowered further into the bath as the evaporation proceeds. Ten c.c. of methyl alcohol are introduced upon the residue, and the evaporation again started. Six such portions of alcohol are thus distilled and 2 c.c. of water are introduced and evaporated between the second and third, as also between the fourth and fifth distillations. If acetic acid is used instead of nitric in the first instance this addition of water is unnecessary.
The distillate is evaporated in the crucible ignited over the blowpipe, cooled in the desiccator for ten minutes and weighed. The increase in weight gives the boron trioxide. The results tend to be from 1 to 2 milligrams too high.
VOLUMETRIC METHOD.
This method is applicable to the indirect determination of boric acid in borax and similar compounds. It is based on the measurement of the quantity of normal solution of acid required to replace the boric acid, and, consequently, is rather a measure of the soda present. The process is an alkalimetric one, and is carried out as follows:—Weigh up 3 grams of the sample and dissolve in water. Tint with methyl orange, and run in from an ordinary burette normal solution of sulphuric acid until a pink tint is got. 100 c.c. of the normal solution of acid are equal to 7.0 grams of boron trioxide (B2O3), or 10.1 grams of anhydrous borax (Na2B4O7).
Examination of Borax.—In addition to the determination just given, the following determinations are also required:—
Water.—Take about 2 grams and heat to tranquil fusion in a platinum crucible. Count the loss in weight as water.
Sulphuric Oxide.—Take 2 grams, dissolve in water, acidify with hydrochloric acid, filter, and precipitate with barium chloride. Wash the precipitate, ignite, and weigh as barium sulphate (see Sulphur).
Chlorine.—Take 2 grams, dissolve in water, acidify with nitric acid, filter, and add silver nitrate. Collect, wash, and weigh the precipitate as silver chloride.
Alumina.—Take 5 or 10 grams, dissolve in water, boil, add ammonia in slight excess, and filter off the precipitate when it has settled. Wash with hot water, ignite, and weigh as alumina (Al2O3).