« AnteriorContinuar »
boils at 700°, forming a vapour whose density is only constant at a temperature of about 1,400°, when it is equal to 79.4 (referred to hydrogen)
-that is, the molecular formula is then Sen, like sulphur at an equally high temperature.
Tellurium is met with still more rarely than selenium (it is known in Saxony) in combination with gold, silver, lead, and antimony in the so-called foliated tellurium ore. Bismuth telluride and silver telluride have been found in Hungary and in the Altai. Tellurium is extracted from bismuth telluride by mixing the finely-powdered ore with potassium and charcoal in as intimate a mixture as possible, and then heating in a covered crucible. Potassium telluride, K,Te, is then formed, because the charcoal reduces potassium tellurite. As potassium telluride is soluble in water, forming a red-brown solution which is decomposed by the oxygen of the atmosphere (K,Te +0+H,O=2KHO+Te), the mass formed in the crucible is treated with boiling water and filtered as rapidly as possible, and the resultant solution exposed to the air, by which means the tellurium is precipitated. So In a free state tellurium has a perfectly metallic appearance ; it is of a silver-white colour, crystallises very easily in long brilliant needles ; is very brittle, so that it can be easily reduced to powder ; but it is a bad conductor of heat and electricity, and in this respect, as in many others, it forms a transition from the metals to the non-metals. Its specific gravity is 6:18, it melts at an incipient red heat, and takes fire when heated in air, like selenium and sulphur, burning with a blue flame, erolving white fumes of tellurous anhydride, TeO2, and emitting an acrid smell if no selenium be present ; but if it be, the odour of the latter preponderates. Alkalis dissolve tellurium when boiled with it, potassium telluride, K,Te, and potassium tellurite, K,Te03, being formed. The solution is of a red colour, owing
forin, but these researches are not so conclusive as those upon soluble silver, and we shall therefore not consider them more fully.
80 The tellurium thus prepared is impure, and contains a large amount of selenium. The latter may be removed by converting the mixture into the salts of potassium, and treating this with nitric acid and barium nitrate, when barium selenate only is precipitated, whilst the barium tellurate remains in solution. This method does not, however, give a pure product, and it appears to be best to separate the selenium from the tellurium in a metallic form; this is done by boiling the impure potassium tellurate with hydrochloric acid, which converts it into potassium tellurite, from which the tellurium is reduced by sulphurous anhydride. The metal thus obtained is then fused and distilled in a stream of hydrogen; the selenium volatilises first, and then the tellurium, owing to its being much less volatile than the former. Nevertheless, tellurium is also volatile, and may be separated in this manner from less volatile metals, such as antimony. Brauner determined the atomic weight of pure tellurium, and found it to be 125, but showed (1889) that tellurium purified by the usual method, even after distillation, contains a large amount of impurities.
to the presence of the telluride, K,Te; but the colour disappears when the solution is cooled or diluted, the tellurium being all precipitated : 2K,Te+K,Te0, +3H,0=6KH0+3Te.pl
81 The decompositlon proceeds in the above order in the cold, but in a hot solution with an excess of potassium hydroxide it proceeds inversely. A similar phenomenon takes place when tellurium is fused with alkalis, and it is therefore necessary in order to obtain potassium telluride to add charcoal.
Selenium and tellurium form higher compounds with chlorine with comparative ease. For selenium, SeCl, and SeCl, are known, and for tellurium TeCl, and TeCl,. The tetrachlorides of selenium and tellurium are formed by passing chlorine over these elements. Selenium tetrachloride, SeCli, is a crystalline, volatile mass which gives selenious anhydride and hydrochloric acid with water. Tellurium tetrachloride is much less volatile, fuses easily, and is also decomposed by water. Both elements form similar compounds with bromine. Tellurium tetrabromide is red, fuses to a brown liquid, volatilises, and gives a crystalline salt, K., Te Bre, 3H.,0, with an aqueous solution of potassium bromide.
CHROMIUM, MOLYBDENUM, TUNGSTEN, URANIUM, AND MANGANESE
Sulphur, selenium, and tellurium belong to the uneven series of the sixth group. In the even series of this group there are known chromium, molybdenum, tungsten, and uranium ; these give acid oxides of the type RO3, like SO3. Their acid properties are less sharply defined than those of sulphur, selenium, and tellurium, as is the case with all elements of the even series as compared with those of the uneven series in the same group. But still the oxides CrO3, M003, WO,, and even U03, have clearly defined acid properties, and form salts of the composition MO,nR03 with bases MO. In the case of the heavy elements, and especially of uranium, the type of oxide, U03, is less acid and more basic, because in the even series of oxides the element with the highest atomic weight always acquires a more and more pronounced basic character. Hence U03 shows the properties of a base, and gives salts U0,X,. The basic properties of chromium, molybdenum, tungsten, and uranium are most clearly expressed in the lower oxides, which they all form. Thus chromic oxide, Cr,0,, is as distinct a base as alumina, Al,03.
Of all these elements chromium is the most widely distributed and the most frequently used. It gives chromic anhydride, Cr0.3, and chromic oxide, Cr.,03—two compounds whose relative amounts of oxygen stand in the ratio 2:1. Chromium is, although somewhat rarely, met with in nature as a compound of one or the other type. The red chromium ore of the Urals, lead chromate or crocoisite PbCr(),, was the source in which chromium was discovered by Vauquelin, who gave it this name (from the Greek word signifying colour) owing to the brilliant colours of its compounds ; the chromates (salts of chromic anhydride) are red and yellow, and the chromic salts (from Cr,03) green and violet. The red lead chromate is, however, a rare chromium ore found only in the Urals and in a few other localities. Chromic oxide, Cr,O3, is more frequently met with. In small quantities it forms the colouring matter of many minerals and rocks-for example, of some serpentines. The commonest ore, and the chief source of the chromium compounds, is the chrome iron ore or chromite, which occurs in the Urals? and Asia Minor, California, Australia, and other localities. This is magnetic iron ore, FeO, Fe2O3, in which the ferric oxide is replaced by chromic oxide, its composition being FeO,Cr,Oz. Chrome iron ore crystallises in octahedra of sp. gr. 4:4 ; it has a feeble metallic lustre, is of a greyish-black colour, and gives a brown powder. It is very feebly acted on by acids, but when fused with potassium acid sulphate it gives a soluble mass, which contains a chromic salt, besides potassium sulphate and ferrous sulphate. In practice the treatment of chrome iron ore is mainly carried on for the preparation of chromates, and not of chromic salts, and therefore we will trace the history of the element by beginning with chromic acid, and especially with the working up of the chrome iron ore into potassium dichromate, K,Cr,0, as the most common salt of this acid. It must be remarked that chromic anhydride, Cr(3, is only obtained in an anhydrous state, and is distinguished for its capacity for easily giving anhydro-salts with the alkalis, containing one, two, and even three equivalents of the anhydride to one equivalent of base. Thus among the potassium salts there is known the normal or yellow chromate, K,Cr(4, which corresponds to, and is perfectly isomorphous with, potassium sulphate, easily forms isomorphous mixtures with it, and is not therefore suitable for a process in which it is necessary to separate the salt from a mixture containing sulphates. As in the presence of a certain excess of acid, the dichromate, K,Cr,0, = 2K,Cr0, + 2HX – 2KX – H,O, is easily formed from K, CrO4, the object of the manufacturer is to produce such a dichromate, the more so as it contains a larger proportion of the elements of chromic acid than the normal salt. Finely-ground chrome iron ore, when heated with an alkali, absorbs oxygen almost as easily (Chapter III., Note 7) as a mixture of the oxides of manganese with an alkali. This absorption is due to the presence of chromic oxide, which is oxidised into the anhydride, and then combines with the alkali Cr,03 + 03 = 2CrOz. As the oxidation and formation of the chromate proceeds, the mass turns yellow. The iron is also oxidised, but does not give ferric acid, because the capacity of the chromium for oxidation is incomparably greater than that of the iron.
A mixture of lime (sometimes with potash) and chrome iron ore is heated in a reverberatory furnace, with free access of air and at a
1 The working of the Ural chrome iron ore into chromium compounds has been firmly established in Russia, thanks to the endeavours of P. K. Ushakoff, who constructed large works for this purpose on the river Kama, near Elabougi, where as much as 2,000 tons of ore are treated yearly, owing to which the importation of chromium preparations into Russia has ceased.
red heat for several hours, until the mass becomes yellow; it then contains normal calcium chromate, CaCrO4, which is insoluble in water in the presence of an excess of lime.bis The resultant mass is ground up, and treated with water and sulphuric acid. The excess of lime forms gypsum, and the soluble calcium dichromate, CaCr,07, together with a certain amount of iron, pass into solution. The solution is poured off, and chalk added to it ; this precipitates the ferric oxide (the ferrous oxide is converted into ferric oxide in the furnace) and forms a fresh quantity of gypsum, while the chromic acid remains in solution - that is, it does not form the sparingly-soluble normal salt (1 part soluble in 240 parts of water). The solution then contains a fairly pure calcium dichromate, which by double decomposition gives other chromates ; for example, with a solution of potassium sulphate it gives a precipitate of calcium sulphate and a solution of potassium dichromate, which crystallises when evaporated.?
Potassium dichromate, K,Cr,Oz, easily crystallises from acid solutions in red, well-formed prismatic crystals, which fuse at a red heat and evolve oxygen at a very high temperature, leaving chromic oxide and the normal salt, which undergoes no further change : 2K,Cr,0,
= 2K,CrO4 + Cr,03 + 0.3. At the ordinary temperature 100 parts of water dissolve 10 parts of this salt, and the solubility increases as the temperature rises. It is most important to note that the dichromate does not contain water, it is K,CrOx + Cr03 ; the acid salt corresponding to potassium acid sulphate, KHSO,, does not exist. It does not even evolve heat when dissolving in water, but on the contrary produces cold, i.e. it does not form a very stable compound with water. The solution and the salt itself are poisonous, and act as powerful oxidising agents, which is the character of chromic acid in general. When heated with sulphur or organic substances, with sulphurous anhydride, hydrogen sulphide, &c., this salt is deoxidised, yielding chromic compounds.2 bis Potassium dichromate 3 is used in the arts and in chemistry as a source for the preparation of all other
1 bis But the calcium chromate is soluble in water in the presence of an excess of chromic acid, as may be seen from the fact that a solution of chromic acid dissolves lime.
2 There are many variations in the details of the manufacturing processes, and these must be looked for in works on technical chemistry. But we may add that the chromate may also be obtained by slightly roasting briquettes of a mixture of chrome iron and lime, and then leaving the resultant mass to the action of moist air (oxygen is absorbed, and the mass turns yellow).
2 bis The oxidising action of potassium dichromate on organic substances at the ordinary temperature is especially marked under the action of light. Thus it acts on gelatin, as Poutven discovered; this is applied to photography in the processes of photo