Chapter VIII: ). Certainly as a fuel-gas the mixture would be less

efficient, and the extra amount of carbon dioxide produced by each flame is not wholly to be ignored. Moreover, since properly generated and purified acetylene can be consumed in proper burners without trouble, all reason for introducing carbon dioxide has disappeared.

MIXTURES OF ACETYLENE AND AIR.--A further proposal for diluting acetylene was the addition to it of air. Apart from questions of explosibility, this method has the advantage over that of adding carbon dioxide that the air, though not inflammable, is, in virtue of its contained oxygen, a supporter of combustion, and is required in a flame; whereas carbon dioxide is not only not a supporter of combustion, but is actually a product thereof, and correspondingly more objectionable. According to some experiments carried out by Dufour, neat acetylene burnt under certain conditions evolved between 1.0 and 1.8 candle-power per litre- hour; a mixture of 1 volume of acetylene with 1 volume of air evolved 1.4 candle-power; a mixture of 1 volume of acetylene with 1.2 volumes of air, 2.25 candle-power; and a mixture of 1 volume of acetylene with 1.3 volumes of air, 2.70 candle-power per litre-hour of acetylene in the several mixtures. Averaging the figures, and calculating into terms of acetylene (only) burnt, Dufour found neat acetylene to develop 1.29 candle-power per litre-hour, and acetylene diluted with air to develop 1.51 candle-power. When, however, allowance is made for the cost and trouble of preparing such mixtures the advantage of the process disappears; and moreover it is accompanied by too grave risks, unless conducted on a largo scale and under most highly skilled supervision, to be fit for general employment.

Fouché, however, has since found the duty, per cubic foot of neat acetylene consumed in a twin injector burner at the most advantageous rate of 3.2 inches, to be as follows for mixtures with air in the proportions stated:

Percentage of air 0 17 27 33.5 Candles per cubic feet 38.4 36.0 32.8 26.0

At lower pressures, the duty of the acetylene when diluted appears to be relatively somewhat higher. Figures which have been published in regard to a mixture of 30 volumes of air and 70 volumes of acetylene obtained by a particular system of producing such a mixture, known as the "Molet- Boistelle," indicate that the admixture of air causes a slight increase in the illuminating duty obtained from the acetylene in burners of various sizes. The type of burner and the pressure employed in these experiments were not, however, stated. This system has been used at certain stations on the "Midi" railway in France. Nevertheless even where the admixture of air to acetylene is legally permissible, the risk of obtaining a really dangerous product and the nebulous character of the advantages attainable should preclude its adoption.

In Great Britain the manufacture, importation, storage, and use of acetylene mixed with air or oxygen, in all proportions and at all pressures, with or without the presence of other substances, is prohibited by an Order in Council dated July 1900; to which prohibition the mixture of acetylene and air that takes place in a burner or contrivance in which the mixture is intended to be burnt, and the admixture of air with acetylene that may unavoidably occur in the first use or recharging of an apparatus (usually a water-to-carbide generator), properly designed and constructed with a view to the production of pure acetylene, are the solitary exceptions.

MIXED CARBIDES.--In fact the only processes for diluting acetylene which possess real utility are that of adding vaporised petroleum spirit or benzene to the gas, as was described in Chapter X. under the name of carburetted acetylene, and one other possible method of obtaining a diluted acetylene directly from the gas-generator, to which a few words will now be devoted. [Footnote: Mixtures of acetylene with relatively large proportions of other illuminating gases, such as are referred to on subsequent pages, are also, from one aspect, forms of diluted acetylene.] Calcium carbide is only one particular specimen of a large number of similar metallic compounds, which can be prepared in the electric furnace, or otherwise. Some of those carbides yield acetylene when treated with water, some are not attacked, some give liquid products, and some yield methane, or mixtures of methane and hydrogen. Among the latter is manganese carbide. If, then, a mixture of manganese carbide and calcium carbide is put into an ordinary acetylene generator, the gas evolved will be a mixture of acetylene with methane and hydrogen in proportions depending upon the composition of the carbide mixture. It is clear that a suitable mixture of the carbides might be made by preparing them separately and bulking the whole in the desired proportions; while since manganese carbide can be won in the electric furnace, it might be feasible to charge into such a furnace a mixture of lime, coke, and manganese oxide calculated to yield a simple mixture of the carbides or a kind of double carbide. Following the lines which have been adopted in writing the present book, it is not proposed to discuss the possibility of making mixed carbides; but it may be said in brief that Brame and Lewes have carried out several experiments in this direction, using charges of lime and coke containing (_a_) up to 20 per cent. of manganese oxide, and (_b_) more than 60 per cent. of manganese oxide. In neither case did they succeed in obtaining a material which gave a mixture of acetylene and methane when treated with water; in case (_a_) they found the gas to be practically pure acetylene, so that the carbide must have been calcium carbide only; in case (_b_) the gas was mainly methane and hydrogen, so that the carbide must have been essentially that of manganese alone. Mixed charges containing between 20 and 60 per cent. of manganese oxide remain to be studied; but whether they would give mixed carbides or no, it would be perfectly simple to mix ready-made carbides of calcium and manganese together, if any demand for a diluted acetylene should arise on a sufficiently large scale. It is, however, somewhat difficult to appreciate the benefits to be obtained from forms of diluted acetylene other than those to which reference is made later in this chapter.

There is, nevertheless, one modification of calcium carbide which, in a small but important sphere, finds a useful _rôle_. It has been pointed out that a carbide containing much calcium phosphide is usually objectionable, because the gas evolved from it requires extra purification, and because there is the (somewhat unlikely) possibility that the acetylene obtained from such material before purification may be spontaneously inflammable. If, now, to the usual furnace charge of lime and coke a sufficient quantity of calcium phosphate is purposely added, it is possible to win a mixture of calcium phosphide and carbide, or, as Bradley, Read, and Jacobs call it, a "carbophosphide of calcium," having the formula Ca_5C_6P_2, which yields a spontaneously inflammable mixture of acetylene, gaseous phosphine, and liquid phosphine when treated with water, and which, therefore, automatically gives a flame when brought into contact with the liquid. The value of this material will be described in Chapter XIII.

GAS-ENRICHING.--Other methods of diluting acetylene consist in adding a comparatively small proportion of it to some other gas, and may be considered rather as processes for enriching that other gas with acetylene. Provided the second gas is well chosen, such mixtures exhibit properties which render them peculiarly valuable for special purposes. They have, usually, a far lower upper limit of explosibility than that of neat acetylene, and they admit of safe compression to an extent greatly exceeding that of acetylene itself, while they do not lose illuminating power on compression. The second characteristic is most important, and depends on the phenomena of "partial pressure," which have been referred to in Chapter VI. When a single gas is stored at atmospheric pressure, it is insensibly withstanding on all sides and in all directions a pressure of roughly 15 lb. per square inch, which is the weight of the atmosphere at sea-level; and when a mixture of two gases, X and Y, in equal volumes is similarly stored it, regarded as an entity, is also supporting a pressure of 15 lb. per square inch. But in every 1 volume of that mixture there is only half a volume of X and Y each; and, ignoring the presence of its partner, each half-volume is evenly distributed throughout a space of 1 volume. But since the volume of a gas stands in inverse ratio to the pressure under which it is stored, the half-volume of X in the 1 volume of X + Y apparently stands at a pressure of half an atmosphere, for it has expanded till it fills, from a chemical and physical aspect, the space of 1 volume: suitable tests proving that it exhibits the properties which a gas stored at a pressure of half an atmosphere should do. Therefore, in the mixture under consideration, X and Y are both said to be at a "partial pressure" of half an atmosphere, which is manifestly 7.5 lb. per square inch. Clearly, when a gas is an entity (either an element or one single chemical compound) partial and total pressure are identical. Now, it has been shown that acetylene ceases to be a safe gas to handle when it is stored at a pressure of 2 atmospheres; but the limit of safety really occurs when the gas is stored at a _partial_ pressure of 2 atmospheres. Neat acetylene, accordingly, cannot be compressed above the mark 30 lb. shown on a pressure gauge; but diluted acetylene (if the diluent is suitable) may be compressed in safety till the partial pressure of the acetylene itself reaches 2 atmospheres. For instance, a mixture of equal volumes of X and Y (X being acetylene) contains X at a partial pressure of half the total pressure, and may therefore be compressed to (2 / 1/2 =) 4 atmospheres before X reaches the partial pressure of 2 atmospheres; and therewith the mixture is brought just to the limit of safety, any effect of Y one way or the other being neglected. Similarly, a mixture of 1 volume of acetylene with 4 volumes of Y may be safely compressed to a pressure of (2 / 1/5 =) 10 atmospheres, or, broadly, a mixture in which the percentage of acetylene is _x_ may be safely compressed to a pressure not exceeding (2 / _x_/100) atmospheres. This fact permits acetylene after proper dilution to be compressed in the same fashion as is allowable in the case of the dissolved and absorbed gas described above.

If the latent illuminating power of acetylene is not to be wasted, the diluent must not be selected without thought. Acetylene burns with a very hot flame, the luminosity of which is seriously decreased if the temperature is lowered. As mentioned in Chapter VIII., this may be done by allowing too much air to enter the flame; but it may also be effected to a certain extent by mixing with the acetylene before combustion some combustible gas or vapour which burns at a lower temperature than acetylene itself. Manifestly, therefore, the ideal diluent for acetylene is a substance which possesses as high a flame temperature as acetylene and a certain degree of intrinsic illuminating power, while the lower the flame temperature of the diluent and the less its intrinsic illuminating power, the less efficiently will the acetylene act as an enriching material. According to Love, Hempel, Wedding, and others, if acetylene is mixed with coal-gas in amounts up to 8 per cent. or thereabouts, the illuminating power of the mixture increases about 1 candle for every 1 per cent. of acetylene present: a fact which is usually expressed by saying that with coal-gas the enrichment value of acetylene is 1 candle per 1 per cent. Above 8 per cent., the enrichment value of acetylene rises, Love having found an increase in illuminating power, for each 1 per cent. of acetylene in the mixture, of 1.42 candles with 11.28 per cent. of acetylene; and of 1.54 candles with 17.62 per cent. of acetylene. Theoretically, if the illuminating power of acetylene is taken at 240 candles, its enrichment value should be (240 / 100 =) 2.4 candles per 1 per cent.; and since, in the case of coal-gas, its actual enrichment value falls seriously below this figure, it is clear that coal-gas is not an economical diluent for it. Moreover, coal-gas can be enriched by other methods much more cheaply than with acetylene. Simple ("blue") water-gas, according to Love, requires more than 10 per cent. of acetylene to be added to it before a luminous flame is produced; while a mixture of 20.3 per cent. of acetylene and 79.7 per cent. of water-gas had an illuminating power of 15.47 candles. Every addition to the proportion of acetylene when it amounted to 20 per cent. and upwards of the mixture had a very appreciable effect on the illuminating power of the latter. Thus with 27.84 per cent. of acetylene, the illuminating power of the mixture was 40.87 candles; with 38.00 per cent. of acetylene it was 73.96 candles. Acetylene would not be an economical agent to employ in order to render water-gas an illuminating gas of about the quality of coal-gas, but the economy of enrichment of water-gas by acetylene increases rapidly with the degree of enrichment demanded of it. Carburetted water-gas which, after compression under 16 atmospheres pressure, had an illuminating power of about 17.5 candles, was enriched by additions of acetylene. 4.5 per cent. of acetylene in the mixture gave an illuminating power of 22.69 candles; 8.4 per cent., 29.54 candles; 11.21 per cent., 35.05 candles; 15.06 per cent., 42.19 candles; and 21.44 per cent., 52.61 candles. It is therefore evident that the effect of additions of acetylene on the illuminating power of carburetted water-gas is of the same order as its effect on coal-gas. The enrichment value of the acetylene increases with its proportion in the mixture; but only when the proportion becomes quite considerable, and, therefore, the gas of high illuminating power, does enrichment by acetylene become economical. Methane (marsh-gas), owing to its comparatively high flame temperature, and to the fact that it has an intrinsic, if small, illuminating power, is a better diluent of acetylene than carbon monoxide or hydrogen, in that it preserves to a greater extent the illuminative value of the acetylene.

Actually comparisons of the effect of additions of various proportions of a richly illuminating gas, such as acetylene, on the illuminative value of a gas which has little or no inherent illuminating power, are largely vitiated by the want of any systematic method for arriving at the representative illuminative value of any illuminating gas. A statement that the illuminating power of a gas is _x_ candles is, strictly speaking, incomplete, unless it is supplemented by the information that the gas during testing was burnt (1) in a specified type of burner, and (2) either at a specified fixed rate of consumption or so as to afford a light of a certain specified intensity. There is no general agreement, even in respect of the statutory testing of the illuminating power of coal-gas supplies, as to the observance of uniform conditions of burning of the gas under test, and in regard to more highly illuminating gases there is even greater diversity of conditions. Hence figures such as those quoted above for the enrichment value of acetylene inevitably show a certain want of harmony which is in reality due to the imperfection or incompleteness of the modes of testing employed. Relatively to another, one gas appears advantageously merely in virtue of the conditions of assessing illuminating power having been more favourable to it. Therefore enrichment values, such as those given, must always be regarded as only approximately trustworthy in instituting comparisons between either different diluent gases or different enriching agents.

ACETYLENE MIXTURES FOR RAILWAY-CARRIAGE LIGHTING.--In modern practice, the gases which are most commonly employed for diluents of acetylene, under the conditions now being considered, are cannel-coal gas (in France) and oil-gas (elsewhere). Fowler has made a series of observations on the illuminating value of mixtures of oil-gas and acetylene. 13.41 per cent. of acetylene improved the illuminating power of oil-gas from 43 to 49 candles. Thirty-nine-candle-power oil-gas had its illuminating power raised to about 60 candles by an admixture of 20 per cent. of acetylene, to about 80 candles by 40 per cent. of acetylene, and to about 110 candles by 60 per cent. of acetylene. The difficulty of employing mixtures fairly rich in acetylene, or pure acetylene, for railway- carriage lighting, lies in the poor efficiency of the small burners which yield from such rich gas a light of 15 to 20 candle-power, such as is suitable for the purpose. For the lighting of railway carriages it is seldom deemed necessary to have a flame of more than 20 candle-power, and it is somewhat difficult to obtain such a flame from oil-gas mixtures rich in acetylene, unless the illuminative value of the gas is wasted to a considerable extent. According to Bunte, 15 volumes of coal-gas, 8 volumes of German oil-gas, and 1.5 volumes of acetylene all yield an equal amount of light; from which it follows that 1 volume of acetylene is equivalent to 5.3 volumes of German oil-gas.

A lengthy series of experiments upon the illuminating power of mixtures of oil-gas and acetylene in proportions ranging between 10 and 50 per cent. of the latter, consumed in different burners and at different pressures, has been carried out by Borck, of the German State Railway Department. The figures show that per unit of volume such mixtures may give anything up to 6.75 times the light evolved by pure oil-gas; but that the latent illuminating power of the acetylene is less advantageously developed if too much of it is employed. As 20 per cent. of acetylene is the highest proportion which may be legally added to oil- gas in this country, Borck's results for that mixture may be studied:

______________________________________________________________________ | | | | | | | | | | | | | | | Propor- | | | | | Consump- | | Consump- | tionate | | Kind of | No. of | Pres- | tion per | Candle- | tion per | Illum- | | Burner. | Burner | sure. | Hour. | Power. | Candle- | inating | | | | mm. | Litres. | | Hour. | Power | | | | | | | Litres. | to Pure | | | | | | | | Oil-Gas.| |___________|________|_______|__________|_________|__________|_________| | | | | | | | | | Bray | 00 | 42 | 82 | 56.2 | 1.15 | 3.38 | | " | 000 | 35 | 54 | 28.3 | 1.91 | 4.92 | | " | 0000 | 35 | 43.3 | 16 | 2.71 | 4.90 | | Oil-gas | | | | | | | | burner | 15 | 24 | 21 | 7.25 | 2.89 | 4.53 | | " " | 30 | 15 | 22 | 10.5 | 2.09 | 3.57 | | " " | 40 | 16 | 33.5 | 20.2 | 1.65 | 3.01 | | " " | 60 | 33 | 73 | 45.2 | 1.62 | 3.37 | | | | The oil-gas from which this mixture was prepared showing: | | | | Bray | 00 | 34 | 73.5 | 16.6 | 4.42 | ... | | " | 000 | 30 | 48 | 6.89 | 6.96 | ... | | " | 0000 | 28 | 39 | 3.26 | 11.6 | ... | | Oil-gas | | | | | | | | burner | 15 | 21 | 19 | 1.6 | 11.8 | ... | | " " | 30 | 14 | 21.5 | 2.94 | 7.31 | ... | | " " | 40 | 15 | 33 | 6.7 | 4.92 | ... | | " " | 60 | 25 | 60 | 13.4 | 4.40 | ... | |___________|________|_______|__________|_________|__________|_________|

It will be seen that the original oil-gas, when compressed to 10 atmospheres, gave a light of 1 candle-hour for an average consumption of 7.66 litres in the Bray burners, and for a consumption of 7.11 litres in the ordinary German oil-gas jets; while the mixture containing 20 per cent. of acetylene evolved the same amount of light for a consumption of 2.02 litres in Bray burners, or of 2.06 litres in the oil-gas jets. Again, taking No. 40 as the most popular and useful size of burner, 1 volume of acetylene oil-gas may be said to be equal to 3 volumes of simple oil-gas, which is the value assigned to the mixture by the German Government officials, who, at the prices ruling there, hold the mixture to be twice as expensive as plain oil-gas per unit of volume, which means that for a given outlay 50 per cent. more light may be obtained from acetylene oil-gas than from oil-gas alone.

This comparison of cost is not applicable, as it stands, to compressed oil-gas, with and without enrichment by acetylene, in this country, owing to the oils from which oil-gas is made being much cheaper and of better quality here than in Germany, where a heavy duty is imposed on imported petroleum. Oil-gas as made from Scotch and other good quality gas-oil in this country, usually has, after compression, an illuminating duty of about 8 candles per cubic foot, which is about double that of the compressed German oil-gas as examined by Borck.

Hence the following table, containing a summary of results obtained by H. Fowler with compressed oil-gas, as used on English railways, must be accepted rather than the foregoing, in so far as conditions prevailing in this country are concerned. It likewise refers to a mixture of oil-gas and acetylene containing 20 per cent. of acetylene.

______________________________________________________________________ | | | | | | | | | | | | | Ratio of | | | |Consumption| |Candles per| Illuminating | | Burner. |Pressure.| per Hour. |Candle| Cubic Foot| Power to that | | | Inches. |Cubic Feet.|Power.| per Hour. |of Oil-gas [1] | | | | | | | in the same | | | | | | | Burner. | |_____________|_________|___________|______|___________|_______________| | | | | | | | | Oil-gas . . | 0.7 | 0.98 | 12.5 | 12.72 | 1.65 | | Bray 000 . | 0.7 | 1.17 | 14.4 | 12.30 | 1.57 | | " 0000 . | 0.7 | 0.97 | 10.4 | 10.74 | 1.41 | | " 00000 | 0.7 | 0.78 | 5.6 | 7.16 | 1.08 | | " 000000 | 0.7 | 0.55 | 1.9 | 3.52 | 1.14 | |_____________|_________|___________|______|___________|_______________|

[Footnote 1: Data relating to the relative pecuniary values of acetylene (carburetted or not), coal-gas, paraffin, and electricity as heating or illuminating agents, are frequently presented to British readers after simple recalculation into English equivalents of the figures which obtain in France and Germany. Such a method of procedure is utterly incorrect, as it ignores the higher prices of coal, coal-gas, and especially petroleum products on the Continent of Europe, which arise partly from geographical, but mainly from political causes.]

The mixture was tried also at higher pressures in the same burners, but with less favourable results in regard to the duty realised. The oil-gas was also tried at various pressures, and the most favourable result is taken for computing the ratio in the last column. It is evident from this table that 1 volume of this acetylene-oil-gas mixture is equal at the most to 1.65 volume of the simple oil-gas. Whether the mixture will prove cheaper under particular conditions must depend on the relative prices of gas-oil and calcium carbide at the works where the gas is made and compressed. At the prevailing prices in most parts of Britain, simple oil-gas is slightly cheaper, but an appreciable rise in the price of gas- oil would render the mixture with acetylene the cheaper illuminant. The fact remains, however, that per unit weight or volume of cylinder into which the gas is compressed, acetylene oil-gas evolves a higher candle- power, or the same candle-power for a longer period, than simple, unenriched British oil-gas. Latterly, however, the incandescent mantle has found application for railway-carriage lighting, and poorer compressed gases have thereby been rendered available. Thus coal-gas, to which a small proportion of acetylene has been added, may advantageously displace the richer oil-gas and acetylene mixtures.

Patents have been taken out by Schwander for the preparation of a mixture of acetylene, air, and vaporised petroleum spirit. A current of naturally damp, or artificially moistened, air is led over or through a mass of calcium carbide, whereby the moisture is replaced by an equivalent quantity of acetylene; and this mixture of acetylene and air is carburetted by passing it through a vessel of petroleum spirit in the manner adopted with air-gas. No details as to the composition, illuminating power, and calorific values of the gas so made have been published. It would clearly tend to be of highly indefinite constitution and might range between what would be virtually inferior carburetted acetylene, and a low-grade air-gas. It is also doubtful whether the combustion of such gas would not be accompanied by too grave risks to render the process useful.