Mitylene

“ As explained in the last chapter, after-generation is the secondary production of acetylene which takes place more or less slowly after the primary reaction is finished, proceeding either between calcium hydroxide, merely damp lime, or damp gas and calcium carbide, with an evolution of more acetylene. As it is possible, and indeed usual, to fit a holder of some capacity even to an automatic generator, the simple fact that more acetylene is liberated after the main reaction is over does not matter, for the gas can be safely stored without waste and entirely without trouble or danger. ”

“ The effects of the products of the polymerisation of acetylene on the flame produced when the gas is burnt at the ordinary acetylene burners have been stated in Chapter VIII., where the reasons therefor have been indicated. The chief primary product of the polymerisation of acetylene by heat appears to be benzene. But there are also produced, in some cases by secondary changes, ethylene, methane, naphthalene, styrolene, anthracene, and homologues of several of these hydrocarbons, while carbon and hydrogen are separated. ”

“ Similarly, the replacement of hydrogen by a water-residue, hydroxyl, gives rise to a phenol. The group of carbon, oxygen, and hydrogen atoms which confers the property of acidity upon an organic compound is a half-molecule of oxalic acid—it is known as the carboxyl group. Thus benzoic acid is the carboxyl-derivative of benzene, and the phthalic acid with which we are now concerned is a dicarboxyl-derivative of benzene. It is related to benzoic acid in the same way that diamidobenzene is related to aniline. ”

“ One peculiar and noteworthy feature of acetylene, often overlooked, is that the apparatus is constructed by men who may have been accustomed to gas-making plant all their lives, and who may understand by mere habit how to superintend a chemical operation; but the same apparatus is used by persons who generally have no special acquaintance with such subjects, and who, very possibly, have not even burnt coal-gas at any period of their lives. ”

“ If a mixture of acetylene with either of the oxides of carbon is led through a red-hot tube, or if a similar mixture is submitted to the action of electric sparks when confined within a closed vessel at some pressure, a decomposition occurs, the whole of the carbon is liberated in the free state, while the hydrogen and oxygen combine to form water. Analogous reactions take place when either oxide of carbon is led over calcium carbide heated to a temperature of 200° or 250° C., the second product in this case being calcium oxide. ”

“ Here again we find scientific research reacting on technology. A few words of chemical explanation will make this manufacture intelligible. By the action of reducing agents on nitro and nitroso-compounds, the nitro and nitroso-group become converted into the amido-group. Thus when nitrobenzene is reduced by iron and an acid we get aniline; similarly when nitrosodimethylaniline is reduced by zinc and an acid we get amidodimethylaniline, and this is the base used in the preparation of methylene blue. By oxidizing this base in the presence of sulphuretted hydrogen, the colouring-matter is formed. ”

“ At atmospheric temperatures and pressure 10 volumes of water dissolve 11 volumes of acetylene, and were the whole of the water in a large generator run to waste often, a sensible loss of gas would ensue. If the carbide falls nearly to the bottom of the water column, the rising gas is forced to bubble through practically the whole of the liquid, so that every opportunity is given it to dissolve in the manner indicated till the liquid is completely saturated. ”

“ If the acetylene is to be evolved from a sample of carbide in order to ascertain how much phosphine the latter yields to the gas, about 50 to 70 grammes of the carbide, of the size of peas, are brought into a half-litre flask, and a tap-funnel, with the mouth of its stem contracted, is passed through a rubber plug fitting the mouth of the flask. A glass tube passing through the plug serves to convey the gas evolved to an absorption apparatus, which is charged with about 75 c.c. of a 2 to 3 per cent. solution of sodium hypochlorite. ”

“ It seems probable, however, that the composition of the ordinary impregnating fluid need not be varied for acetylene mantles provided it is of the proper strength and the mantles are raised to a higher temperature in manufacture than coal-gas mantles by the use of either coal-gas at very high pressure or an acetylene flame. The thickness of the substance of the mantle cannot be greatly increased with a view to attaining greater stability without causing a reduction in the light afforded. ”

“ As acetylene is endothermic and evolves much heat on decomposition, and as that heat must primarily be communicated to the hydrogen, it follows that the latter must be much hotter than the original acetylene; the hydrogen accordingly strives to fill a much larger space than that occupied by the undecomposed gas, and if that gas is contained in a closed vessel, considerable internal pressure will be set up, which may or may not cause the vessel to burst. ”

“ During the operation of an acetylene generator a large amount of heat is produced, the quantity of which is beyond human control. It is desirable, for various reasons, that the temperature shall be kept as low as possible. There are three substances present to which the heat may be compelled to transfer itself until it has opportunity to pass into the surrounding atmosphere: the material of which the apparatus is constructed, the gas which is in process of evolution, and whichever of the two bodies-- calcium carbide or water--is in excess in the generator. ”

“ Inasmuch as acetylene is produced by the mere interaction of calcium carbide and water, that is to say, by simply bringing those two substances in the cold into mutual contact within a suitable closed space, and inasmuch as calcium carbide can always be purchased by the consumer in a condition perfectly fit for immediate decomposition, the preparation of the gas, at least from the theoretical aspect, is characterised by extreme simplicity. ”

“ If, for example, the quantity of water present in a generator is more than chemically sufficient to attack all the carbide added, however largo or small that excess may be, no more, and, theoretically speaking, no less, acetylene can ever be evolved than 26 parts by weight of gas for every 64 parts by weight of calcium carbide consumed. ”

“ Nevertheless, although satisfactory medium-sized vehicular lamps for the generation of acetylene have been constructed, the best way of using acetylene for all such employments as these is to carry it ready made in a state of compression. For railway purposes, where an oil-gas plant is in existence, and where it is merely desired to obtain a somewhat brighter light, the oil-gas may be enriched with 20 per cent. of acetylene, and the mixed gas pumped into the same cylinders to a pressure of 10 atmospheres, as mentioned in Chapter XI. ”

“ The high proportion of carbon dioxide and the low proportion of oxygen in chimney gases makes a mixture of acetylene and chimney gases non-explosive in any proportions, and hence if the air is first wholly or to a large extent expelled from a pipe, main, or apparatus, by means of chimney gases, acetylene may be admitted, and a much shorter time allowed for the expulsion by it of the contents of the pipe, before a light is applied at the burners, &c. ”

“ From surgery back to colouring-matters, and from these to pharmaceutical preparations and perfumes, are we led in following up the cycles of chemical transformation which these tar-products have undergone in the hands of the technologist, guided by the researches of the chemist. It was observed by Runge in 1834 that crude carbolic acid, on treatment with lime, gave a red, acid colouring-matter which he separated and named “rosolic acid.” The observation was followed up, and many other chemists obtained red colouring-matters by the oxidation of crude phenol. ”

“ But the most interesting and most promising of all is the complete inorganic synthesis that dispenses with the aid of vegetation and starts with coal and lime. These heated together in the electric furnace form calcium carbide and this, as every automobilist knows, gives acetylene by contact with water. From this gas isoprene can be made and the isoprene converted into rubber by sodium, or acid or alkali or simple heating. Acetone, which is also made from acetylene, can be converted directly into rubber by fuming sulfuric acid. ”

“ Properties of the hydrocarbons. The lower members of the first two series of hydrocarbons mentioned are all gases; the succeeding members are liquids. In some series, as the methane series, the higher members are solids. The preparation and properties of methane and acetylene have been discussed in a previous chapter. Ethylene is present in small quantities in coal gas and may be [Pg 401] obtained in the laboratory by treating alcohol (C2H6O) with sulphuric acid:
C2H6O = C2H4 + H2O.
Benzene, the first member of the benzene series, is a liquid boiling at 80°. ”

“ An apparatus has been constructed in France on the lines of some portable fire-extinguishing appliances in which the pressure set up by the evolution of acetylene in a closed space produces a spray of water charged with lime and gas under the pressure obtaining; the liquid being thrown over growing vines or other plants in order to destroy parasitic and other forms of life. The apparatus consists of a metal cylinder fitted with straps so that it can be carried by man or beast. ”

“ When brought in contact, the oxygen in the water decomposes the calcium in the carbide, and in this decomposition the hydrogen in the water is liberated and unites with the carbon of the carbide, forming a hydrocarbon gas which is acetylene. It is a pure white light of intense brilliancy and high candlepower. The spectrum analysis of acetylene shows that it is almost identical with sunlight, and in consequence delicate shades of color appear according to their true value as under the light of the sun, consequently it penetrates fog to a greater distance than other lights. ”

“ The consumption of acetylene is about 75 litres per hour for each millimetre of thickness in the sheet treated, and the normal consumption of oxygen is 1.7 times as much; a joint 6 metres long can be burnt in 1 millimetre plate per hour, and one of 1.5 metres in 10 millimetre plate. In certain cases it is found economical to raise the metal to dull redness by other means, say with a portable forge of the usual description, or with a blowpipe consuming coal-gas and air. ”

“ It will be seen that a sufficient removal of these generator impurities need throw no appreciable extra labour upon the consumer of acetylene, for he can readily select a type of generator in which their production is reduced to a minimum; while a cotton-wool or coke filter for the gas, a water washer, which is always useful in the plant if only employed as a non-return valve between the generator and the holder, and the indispensable chemical purifiers, will take out of the acetylene all the remaining generator impurities which need, and can, be extracted. ”

“ IMPURITIES OF ACETYLENE.--Combining together what may be termed the carbide impurities and the generator impurities in crude acetylene, the foreign bodies are partly gaseous, partly liquid, and partly solid. They may render the gas dangerous from the point of view of possible explosions; they, or the products derived from them on combustion, may be harmful to health if inspired, injurious to the fittings and decorations of rooms, objectionable at the burner orifices by determining, or assisting in, the formation of solid growths which distort the flame and so reduce its illuminating power ”

“ In an automatic apparatus, the fundamental idea is that the generating chamber, or one at least of several generating chambers, shall always contain a considerable quantity of undecomposed carbide, and some receptacle always contain a store of water ready to attack that carbide, so that whenever a demand for gas shall arise everything may be ready to meet it. Inasmuch as acetylene is an inflammable gas, it possesses all the properties characteristic of inflammable gases in general ”

“ If the temperature of an acetylene generator rises to such an extent that part of the gas is polymerised into tar, that tar naturally tends to coat the residual carbide lumps, and, being greasy in character, more or less completely protects the interior from further attack. ”

“ In practice this phenomenon of a secondary production of gas, which is known as "after-generation," is regularly met with in all generators where the carbide is in excess of the water added; but the amount of acetylene so evolved rarely exceeds one-quarter or one-third of the main make. The actual amount evolved and the rate of evolution depend, not merely upon the quantity of undecomposed carbide still remaining in contact with the damp lime, but also upon the rapidity with which carbide naturally decomposes in presence of liquid water, and the size of the lumps. ”

“ I have many times observed how quickly, and, indeed, almost instantaneously, small animals recover from the stupor occasioned by certain permanent gases which are sparingly soluble in watery fluids, as olefiant gas, carbonic oxide and carbonic acid gases, nitrous oxide and the gaseous oxide of methyle. Now amylene is so volatile as to approach to a permanent gas; at a temperature a little above that of the human body it would be a gas, and the vapour is very sparingly soluble in watery fluids, and consequently in the blood. Sulphuric ether is, indeed, as volatile as amylene. ”