A Text-book of Assaying: For the Use of Those Connected with Mines Part 54

When the ammonia in 50 c.c. has been determined, that in the whole solution is ascertained by a suitable multiplication. By 10, for example, if the bulk was 500 c.c., or by 20 if it was a litre.

Distilled water is used throughout. It must be free from ammonia; and is best prepared by distilling an ammonia-free spring water.

FOOTNOTES:

[90] Al_{2}Cl_{6} + 3Na_{2}S_{2}O_{3} + 3H_{2}O = Al_{2}(HO)_{6} + 6NaCl + 3S + 3SO_{2}

[91] 3BeO,Al_{2}O_{3},6SiO_{2}

[92] CaC_{2}O_{4} = CaCO_{3}+CO.

[93] Resolved into two with a powerful spectroscope.

[94] Ammonium compounds are frequently produced when dissolving metals in nitric acid; or when nitrates are heated in the presence of the metals.

PART III--NON-METALS.

CHAPTER XV.

OXYGEN AND OXIDES.--THE HALOGENS.

OXYGEN.

Oxygen occurs in nature in the free state, forming 23 per cent. by weight, or 21 per cent. by volume of the atmosphere; but, since it is a gas, its presence is easily overlooked and its importance underestimated. Except in the examination of furnace-gases, &c., the a.s.sayer is not often called upon to determine its quant.i.ty, but it forms one of his most useful reagents, and there are many cases where he cannot afford to disregard its presence. It occurs not only in the air, but also dissolved in water; ordinary waters containing on an average 0.00085 per cent. by weight, or 0.85 parts per 100,000.

Chemically, it is characterised by its power of combining, especially at high temperatures, with the other elements, forming an important cla.s.s of compounds called oxides. This combination, when rapid, is accompanied by the evolution of light and heat; hence oxygen is generally called the supporter of combustion. This property is taken advantage of in the operation of calcining, scorifying, cupelling, &c. The importance of a free access of air in all such work is seen when it is remembered that 1 litre of air contains 0.2975 gram of oxygen, and this quant.i.ty will only oxidise 0.1115 gram of carbon, 0.2975 gram of sulphur, or 3.849 grams of lead.

Oxidation takes place at the ordinary temperature with many substances.

Examples of such action are seen in the weathering of pyrites, rusting of iron, and (in the a.s.say office) the weakening of solutions of many reducing agents.

For methods of determining the percentage of oxygen in gases, for technical purposes, the student is referred to Winkler & Lunge's "Technical Gas a.n.a.lysis."

OXIDES.

Oxides are abundant in nature, almost all the commonly occurring bodies being oxidised. Water (H_{2}O) contains 88.8 per cent. of oxygen; silica, lime, alumina, magnesia, and the other earths are oxides, and the oxides of the heavier metals are in many cases important ores; as, for example, ca.s.siterite (SnO_{2}), haemat.i.te (Fe_{2}O_{3}), magnet.i.te (Fe_{3}O_{4}), and pyrolusite (MnO_{2}). In fact, the last-named mineral owes its value to the excess of oxygen it contains, and may be regarded as an ore of oxygen rather than of manganese.

Most of the metals, when heated to redness in contact with air, lose their metallic l.u.s.tre and become coated with, or (if the heating be prolonged) altogether converted into, oxide. This oxide was formerly termed a "calx," and has long been known to weigh more than the metal from which it was obtained. For example, one part by weight of tin becomes, on calcining, 1.271 parts of oxide (putty powder). The student will do well to try the following experiments:--Take 20 grams of tin and heat them in a m.u.f.fle on a scorifier, sc.r.a.ping back the dross as it forms, and continuing the operation until the whole of the metal is burnt to a white powder and ceases to increase in weight.[95] Take care to avoid loss, and, when cold, weigh the oxide formed. The oxide should weigh 25.42 grams, which increase in weight is due to the oxygen absorbed from the air and combined with the metal. It can be calculated from this experiment (if there has been no loss) that oxide of tin contains 21.33 per cent. of oxygen and 78.67 per cent. of tin. Oxidation is performed with greater convenience by wet methods, using reagents, such as nitric acid, which contain a large proportion of oxygen loosely held. Such reagents are termed oxidising agents. Besides nitric acid, permanganate of potash, bichromate of potash, and peroxide of hydrogen are largely used for this purpose. One c.c. of nitric acid contains as much oxygen as 2.56 litres of air, and the greater part of this is available for oxidising purposes. Try the following experiment:--Take 2 grams of tin and cover in a weighed Berlin dish with 20 c.c. of dilute nitric acid, heat till decomposed, evaporate to dryness, ignite, and weigh. The 2 grams of tin should yield 2.542 grams of oxide. The increase in weight will be proportionally the same as in the previous experiment by calcination, and is due to oxygen, which in this case has been derived from the nitric acid.

The percentage of oxygen in this oxide of tin (or in any of the oxides of the heavier metals) may be directly determined by heating such oxides in a current of hydrogen, and collecting and weighing the water formed.

It is found by experiment that 88.86 parts by weight of oxygen, combining with 11.14 parts of hydrogen, form 100 parts of water; so that from the weight of water formed it is easy to calculate the amount of oxygen the oxide contained.

[Ill.u.s.tration: FIG. 62.]

Take 1 gram of the dried and powdered oxide and place it in a warm dry combustion tube. Place the tube in a furnace, and connect at one end with a hydrogen apparatus provided with a sulphuric acid bulb for drying the gas, and at the other with a weighed sulphuric acid tube for collecting the water formed. The apparatus required is shown in fig. 62.

Pa.s.s hydrogen through the apparatus, and, when the air has been cleared out, light the furnace. Continue the heat and current of hydrogen for half an hour (or longer, if necessary). Allow to cool. Draw a current of dry air through the weighed tube. Weigh. The increase in weight gives the amount of water formed, and this, multiplied by 0.8886, gives the weight of the oxygen. The percentage of oxygen thus determined should be compared with that got by the oxidation of the metal. It will be practically the same. The following results can be taken as examples:--

Twenty grams of tin, calcined as described, gave 25.37 grams of oxide.

Two grams of tin, oxidised with nitric acid and ignited, gave 2.551 grams of oxide.

One gram of the oxide of tin, on reduction in a current of hydrogen, gave 0.2360 gram of water (equivalent to 0.2098 gram of oxygen), and left 0.7900 gram of metal.

Ten grams of ferrous sulphate gave, on strong ignition, 2.898 grams of ferric oxide (Fe_{2}O_{3})[96] instead of 2.877.

The student should similarly determine the percentage of oxygen in oxides of copper and iron. The former oxide may be prepared by dissolving 5 grams of copper in 50 c.c. of dilute nitric acid, evaporating to dryness, and strongly igniting the residue. The oxide of iron may be made by weighing up 10 grams of powdered ferrous sulphate (= to 2.014 grams of iron) and heating, at first gently, to drive off the water, and then at a red heat, until completely decomposed. The weight of oxide, in each case, should be determined; and the percentage of oxygen calculated. Compare the figures arrived at with those calculated from the formula of the oxides, CuO and Fe_{2}O_{3}.

It would be found in a more extended series of experiments that the same metal will, under certain conditions, form two or more oxides differing among themselves in the amount of oxygen they contain. These oxides are distinguished from one another by such names as "higher" and "lower oxides," "peroxides," "protoxides," "dioxides," &c.

The oxides may be conveniently cla.s.sified under three heads:--

(1) _Those that are reduced to metal by heat alone_, such as the oxides of mercury, silver, platinum, gold, &c.;

(2) _Those which are reduced by hydrogen at a red heat_, which includes the oxides of the heavy metals;

(3) _Those which are not reduced by these means_, good examples of which are silica, alumina, the alkalies, and the alkaline earths.

Another important cla.s.sification is into acid, basic and neutral oxides.

The oxides of the non-metallic elements, such as sulphur, carbon, phosphorus, &c., are, as a rule, acid; and the more oxygen they contain, the more distinctly acid they are. The oxides of the metals are nearly all basic; and, as a rule, the less oxygen they contain, the more distinctly basic they are.

The basic oxides, which are soluble in acids, give rise to the formation of salts when dissolved therein. During the solution, water is formed, but no gas is evolved. The oxide dissolved in each case neutralizes an equivalent of the acid used for solution.[97] The basic properties of many of these can be taken advantage of for their determination. This is done in the case of soda, potash, lime, &c., by finding the quant.i.ty of acid required to neutralize a given weight of the substance.

There are some oxides which, under certain conditions, are acid to one substance (a stronger base) and basic to another (a stronger acid). For example, the oxides of lead and of tin, as also alumina, dissolve in caustic soda, acting as acids; whilst, on the other hand, they combine with sulphuric or hydrochloric acid, playing the part of bases.

The oxides known as "earths," when ignited, are many of them insoluble in acids, although easily dissolved before ignition.

It is common in complete a.n.a.lyses of minerals to meet with cases in which the sum total of the elements found falls short of the amount of ore taken; and here oxygen must be looked for. For example, this occurs in the case of a mixture of pyrites with oxide of iron, or in a mixture of sulphides and sulphates. The state in which the elements are present, and the percentage (say of sulphides and sulphates) can in many cases be determined; but this is not always required. When the difference between the sum total and the elements found is small, it is reported as "oxygen and loss." When, however, it is considerable, the oxygen may be reported as such; and its amount be either determined directly in the way already described, or calculated from the best determination that can be made of the relative amounts of oxides, sulphides, sulphates, &c., present. Such cases require a careful qualitative a.n.a.lysis to find out that the substance is present; and then the separation of each const.i.tuent is made as strictly as possible. These remarks apply especially to ores of the heavy metals. The separation of the const.i.tuents is effected with suitable solvents applied in proper order. The soluble sulphates, for example, are extracted with water; the oxides by the dilute acids or alkalies in which they are known to be soluble. The oxygen in the sulphates and oxides thus obtained is estimated by determining the sulphur and metals in the solutions, and calculating the amount of oxygen with which they combine. The metals of the earths and alkalies are almost invariably present as oxides, and are reported as such; except it is known that they are present in some other form, such as fluoride or chloride. Thus, silica, alumina, lime, water, &c., appear in an a.n.a.lysis; even in those cases where "oxygen and loss" is also mentioned. As an example of such a report, take the following a.n.a.lysis of Spanish pyrites:--

Sulphur 49.00 Iron 43.55 Copper 3.20 a.r.s.enic 0.47 Lead 0.93 Zinc 0.35 Lime 0.10 Silica, &c. 0.63 Water 0.70 Oxygen and loss 1.07 ----- 100.00

The following example will ill.u.s.trate the mode of calculating and reporting. A mineral, occurring as blue crystals soluble in water, and found on testing to be a mixed sulphate of iron and copper, gave on a.n.a.lysis the following results:--

Water 44.51 per cent.

Sulphuric oxide 28.82 "

Copper 8.44 "

Ferrous iron 11.81 "

Ferric iron 0.38 "

Zinc 0.28 "

----- 94.24