Flame
FLAME (Lat. flamma; the root flag-appears in flagrare, to burn, blaze, and Gr. ). There is no strict scientific definition of flame, but for the purpose of this article it will be regarded as a name for gas which is temporarily luminous in consequence of chemical action. It is well known that the luminosity of gases can be induced by the electrical discharge, and with rapidly alternating high-tension discharges in air an oxygen-nitrogen flame is produced which is long and flickering, can be blown out, yields nitrogen peroxide, and is in fact indistinguishable from an ordinary flame except by its electrical mode of maintenance. The term "flame" is also applied to solar protuberances, which, according to the common view, consist of gases whose glow is of a purely thermal origin. Even with the restricted definition given above, difficulties present themselves. It is found, for example, with a hydrogen flame that the luminosity diminishes as the purity of the hydrogen is increased and as the air is freed from dust, and J.S. Stas declared that under the most favourable conditions he was only able, even in a dark room, to localize the flame by feeling for it, an observation consistent with the fact that the line spectrum of the flame lies wholly in the ultra-violet. On the other hand, there are many examples of chemical combination between gases where the attendant radiation is below the pitch of visibility, as in the case of ethylene and chlorine. It will be obvious from these facts that a strict definition of flame is hardly possible. The common distinction between luminous and non-luminous flames is, of course, quite arbitrary, and only corresponds to a rough estimate of the degree of luminosity.
The chemical energy necessary for the production of flame may be liberated during combination or decomposition. A single substance like gun-cotton, which is highly endothermic and gives gaseous products, will produce a bright flame of decomposition if a single piece be heated in an evacuated flask. Combination is the more common case, and this means that we have two separate substances involved. If they be not mixed en masse before combination, the one which flows as a current into the other is called conventionally the "combustible," but the simple experiment of burning air in coal gas suffices to show the unreality of this distinction between combustible and supporter of combustion, which, in fact, is only one of the many partial views that are explained and perhaps justified by the dominance of oxygen in terrestrial chemistry.
Although hydrocarbon flames are the commonest and most interesting, it will be well to consider simpler flames first in order to discuss some fundamental problems. In hydrocarbon flames the complexity of the combustible, its susceptibility to change by heating, and the possibilities of fractional oxidation, create special difficulties. In the flame of hydrogen and oxygen or carbon monoxide and oxygen we have simpler conditions, though here, too, things may be by no means so simple as they seem from the equations 2H2 + O2 = 2H2O and 2CO + O2 = 2CO2. The influence of water vapour on both these actions is well known, and the molecular transactions may in reality be complicated. We shall, however, assume for the sake of clearness that in these cases we have a simple reaction taking place throughout the mass of flame. There are various ways in which a pair of gases may be burned, and these we shall consider separately. Let us first suppose the two gases to have been mixed en masse and a light to be applied to the stationary mixture. If the mixture be made within certain limiting proportions, which vary for each case, a flame spreads from the point where the light is applied, and the flame traverses the mixture. This flame may be very slow in its progress or it may attain a velocity of the order of one or two thousand metres per second. Until comparatively recent times great misunderstanding prevailed on this subject. The slow rate of movement of flame in short lengths of gaseous mixtures was taken to be the velocity of explosion, but more recent researches by M.P.E. Berthelot, E. Mallard and H.L. le Chatelier and H.B. Dixon have shown that a distinction must be made between the slow initial rate of inflammation of gaseous mixtures and the rapid rate of detonation, or rate of the explosive wave, which in many cases is subsequently set up. We shall here deal only with the slow movements of flame. The development of a flame in such a gaseous mixture requires that a small portion of it should be raised to a temperature called the temperature of ignition. Here again considerable misunderstanding has prevailed. The temperature of ignition has often been regarded as the temperature at which chemical combination begins, whereas it is really the temperature at which combination has reached a certain rate. The combination of hydrogen and oxygen begins at temperatures far below that of ignition. It may indeed be supposed that the combination occurs with extreme slowness even at ordinary temperatures, and that as the temperature is raised the velocity of the reaction increases in accordance with the general expression according to which an increase of 10°C. will approximately double the rate. However that may be, it has been proved experimentally by J.H. van't Hoff, Victor Meyer and others that the combination of hydrogen and oxygen proceeds at perceptible rates far below the temperature of ignition. The phenomenon appears to be greatly influenced by the solid surfaces which are present; thus in a plain glass vessel the combination only began to be perceptible at 448°, whilst in a silvered glass vessel it would be detected at 182°C.
The same kind of thing is true for most oxidizable substances, including ordinary combustibles. We must look upon the application of heat to a combustible mixture as resulting in an increase of the rate of combination locally. Let us suppose that we are dealing with a stratum of the mixture in small contiguous sections. If we raise the temperature of the first section a°C., an increased rate of combination is set up. The heat produced by this combination will be dissipated by conduction and radiation, and we will suppose that it does not quite suffice to raise the adjacent section of the mixture to a°C. The combination in that section, therefore, will not be as rapid as in the first one, and so evidently the impulse to combination will go on abating as we pass along the stratum. Suppose now we start again and heat the first section of the mixture to a temperature c°C., such that the rate of combination is very rapid and the heat developed by combination suffices to raise the adjacent section of the mixture to a temperature higher than c°C. The rate of combination will then be greater than in the first section, and the impulse to combination will be intensified in the same way from section to section along the stratum until a maximum temperature is reached. It is obvious that there must be a temperature of b°C. between a° and c° which will satisfy this condition, that the heat which results from the combination stimulated in the first section just suffices to raise the temperature of the second section to b°. This temperature b° is the temperature of ignition of the mixture; so soon as it is attained by a portion of the mixture the combustion becomes self-sustaining and flame spreads through the mixture. Ignition temperature may be defined briefly as the temperature at which the initial loss of heat due to conduction, etc., is equal to the heat evolved in the same time by the chemical reaction (van't Hoff). From the above considerations we see that the temperature of ignition will vary not only when the gases are varied, but when the proportions of the same gases are varied, and also when the pressure is varied. We can see also that outside certain limiting proportions a mixture of gases will have no practicable ignition temperature, that is to say, the cooling effect of the gas which is in excess will carry off so much heat that no attainable initial heating will suffice to set up the transmission of a constant temperature. Thus in the case of hydrogen and air, mixtures containing less than 5 and more than 72% of hydrogen are not inflammable. The theory of ignition temperature enables us to understand why in an explosive mixture a very small electric spark may not suffice to induce explosion. Combination will indeed take place in the path of the spark, but the amount of it is not sufficient to meet the loss of heat by conduction, etc. It must be added that the theory of ignition temperatures given above does not explain all the observed facts. F. Emich states that the inflammability of gaseous mixtures is not necessarily greatest when the gases are mixed in the proportions theoretically required for complete combination, and the influence of foreign gases does not appear to follow any simple law. The presence of a small quantity of a gas may exercise a profound influence on the ignition temperature as in the case of the addition of ethylene to hydrogen (Sir Edward Frankland), and again when a mixture of methane and air is raised to its ignition temperature a sensible interval (about 10 seconds) elapses before inflammation occurs.
The rate at which a flame will traverse a mixture of two gases which has been ignited depends on the proportions in which the gases are mixed. Fig. 1 (Bunte) represents this relationship for several common gases.
Fig. 1. - Rates of inflammation of combustible gases with air.
Fig. 2.
If a ready-made gaseous mixture is to be used for the production of a steady flame, it may be forced through a tube and ignited at the end; it is obvious that the velocity of efflux must be greater than the initial rate of inflammation of the mixture, for otherwise the mixture would fire back down the tube. If the velocity of efflux be considerably greater than the rate of inflammation, the flame will be separated from the end of the tube, and only appear as a flickering crown where the velocity and inflammability of the issuing gas have been diminished by admixture with air. With much increased velocity of efflux the flame will be blown out. J.B.A. Dumas used to show the experiment of blowing out a candle with electrolytic gas. A steady flame formed by burning a ready-made gaseous mixture at the end of a tube of circular section has the form shown in fig. 2. The small internal cone marks the lower limiting surface of the flame; it is the locus of all points where the velocity of efflux is just equal to the velocity of inflammation, and its conical form is explained by the fact that the rate of efflux of gas is greatest in the vertical axis of the tube where the flow is not retarded by friction with the walls, as well as by the further fact that the gas issuing from such an orifice spreads outwards, the inflammation proceeding directly against it. The flame, it will be seen, is of considerable thickness. If the gaseous mixture be hydrogen and oxygen, or carbon monoxide and oxygen, it will have no obvious features of structure beyond those shown in the figure; that is to say, the shaded region of burning gas has the appearance of homogeneity and uniform colour which might be expected to accompany a uniform chemical condition. Some admixture of the external air will, of course, take place, especially in the upper parts of the flame, and detectable quantities of oxides of nitrogen may be found in the products of combustion, but this is an inconsiderable feature. The flame just described is essentially that of a blowpipe.
A second way of producing a flame is the more common one of allowing one gas to stream into the other. Using the same gases as before, hydrogen or carbon monoxide with oxygen, we find again that the flame is conical in form and uniform in colour, but in this case, if the velocity of efflux be not immoderate, the burning gas only extends over a comparatively thin shell, limited on the inside by the pure combustible and on the outside by a mixture of the products of combustion with oxygen. The combustible gas has to make its own inflammable mixture with the circumambient oxygen, and we may suppose the column of gas to be burned through as it ascends. The core of unburned gas thus becomes thinner as it ascends and the flame tapers to a point. The external surface of a flame of this kind will for the same consumption of gas be larger than that of a flame where the ready-made mixture of gases is used. If a jet of one gas be sent with a sufficient velocity into another, turbulent admixture takes place and an unsteady sheet of flame of uniform colour is obtained.
A third way of forming a flame is to allow the whole of one gas, mixed with a less quantity of the second than is sufficient for complete combustion, to issue into an atmosphere of the second. This is the case with what are generally known as atmospheric burners, of which the Bunsen burner is the prototype. The development of a flame of this kind can be well studied in the case of carbon monoxide and air. The carbon monoxide is fed into a Bunsen burner with closed air-valve, the burner-tube being prolonged by affixing a glass tube to it by means of a cork. The flame consists of a single conical blue sheet. If now the air-valve be opened very slightly, an internal cone of the same blue colour makes its appearance. The air which has entered through the air-valve ("primary" air) has become mixed with the carbon monoxide and so oxidizes its quota in an internal cone, the rest of the carbon monoxide (diluted now, of course, with carbon dioxide and nitrogen) wandering into the external atmosphere to burn (with "secondary" air) in a second cone. The existence of the internal cone and the subsequent thermal effect lead to slight convexity of surface in the outer cone. If the quantity of primary air be increased more internal combustion can take place. This, however, does not lead to an enlargement of the inner cone, for the increase of air increases the rate of inflammation of the mixture, and the inner cone (which only maintains its stability because the rate of efflux of the mixture is greater than the velocity of inflammation) contracts, and will, as the proportion of primary air is increased, soon evince a tendency to enter the burner-tube. At this stage an interesting phenomenon is to be noticed. When we have reached the point of aeration where the velocity of inflammation of the mixture just surpasses the velocity of efflux, the inner cone enters the burner-tube as a disk and descends, but this downward motion checks the suction flow of air through the valve at the base of the burner, whilst it does not appreciably check the pressure flow of the carbon monoxide through the gas nozzle. The result is that a stratum of gas-mixture poor in air, and therefore of low rate of inflammation, is formed, and when the descending disk of flame meets it, the descent is arrested and the disk returns to the top of the tube, reproducing the inner cone. The full air suction is now restored and the course of events is repeated. This oscillatory action can be maintained almost indefinitely long if the pressure and other conditions be maintained constant. With still more primary air the inner cone of flame simply fires back to the burner nozzle, or, in the last stage, we may have enough air entering to produce a flame of the blast blowpipe type, namely, one where the carbon monoxide mixed with an excess of primary air burns with a single cone in a steady flame.
By means of a simple contrivance devised by A. Smithells a two-coned flame of the kind described may be resolved into its components. The apparatus is like a half-extended telescope made of two glass tubes, and it is evident that the velocity of a mixture of gases flowing through it must be greater in the narrow tube than in the wider one. If the end of the narrower tube be fixed to a Bunsen burner and the flame be formed at the end of the wider one, then when the air-supply is increased to a certain point the inner cone will descend into the wide tube and attach itself to the upper end of the narrower one. This occurs when the velocity of inflammation is just greater than the upward velocity of the gaseous stream in the wide tube and less than the upward velocity in the narrow tube. If the outer tube be now drawn down, a two-coned flame burns at the end of the inner tube; if the outer tube be slid up again, it detaches the outer cone and carries it upward. This apparatus has been of use in investigating the progress of combustion in various flames.
Temperature of Flames. - The term "flame-temperature" is used very vaguely and has no clear meaning unless qualified by some description. It is least ambiguous when used in reference to flames where the combining gases are mixed in theoretical proportions before issuing from the burner. The flame in such a case has considerable thickness and uniformity, and, though the temperature is not constant throughout, flames of this type given by different combustibles admit of comparison. In other flames where the shells of combustion are thin and envelop large regions of unburned or partly-burned gas, it is not clear how temperature should be specified. An ordinary gas-flame will not, from the point of view of the practical arts, give a sufficient temperature for melting platinum, yet a very thin platinum wire may be melted at the edge of the lower part of such a flame. The maximum temperature of the flame is therefore not in any serious sense an available temperature. It will suffice to point out here that in order to burn a gas so that it may have the highest available temperature, we must burn it with the smallest external flame-surface obtainable. This is done when the combining gases are completely mixed before issuing from the burner. Where this is impracticable we may employ a burner of the Bunsen type, and arrange matters so that a large amount of primary air is supplied. It is in this direction that modern improvements have been made with a view to obtaining hot flames for heating the Welsbach mantle. The Kern burner, for example, employs the principle of the Venturi tube. Where much primary air is drawn in it is usual to provide for it being well mixed with the gas, otherwise an unsteady flame may be produced with a great tendency to light back. The burner head is therefore usually provided with a mixing chamber and the mixture issues through a slit or a mesh. A great many modified Bunsen burners have been produced, the aim in all of them being to produce a flame which shall combine steadiness with the smallest attainable external surface.
To estimate the temperature of flames several methods have been employed. The method of calculation, based on the supposition that the whole heat of combustion is localized in the product (or products) of combustion and heats it to a temperature depending on its specific heat, cannot be applied in a simple way. Apart from the assumption (which there is reason to suppose incorrect) that none of the chemical energy assumes the radiant form directly, we have to regard the possible change of specific heat at high temperatures, the likelihood of dissociation and the time of reaction. Any practical consideration of temperature must have regard to a large assemblage of molecules and not to a single one, and therefore any influence which means delay in combination will result in reduction of temperature by radiation and conduction. It can hardly be maintained that in the present state of knowledge we have the requisite data for the calculation of flame temperature, though good approximations may be made. Many attempts have been made to determine flame temperatures by means of thermo-electric couples and by radiation pyrometers. The couple most employed is that known as H.L. le Chatelier's, consisting of two wires, one of platinum and the other an alloy of 90% platinum and 10% of rhodium. When all possible precautions are taken it is possible by means of such thermo-couples to measure local flame temperatures with a considerable degree of accuracy. Subjoined are some results obtained at different times and by different observers with regard to the maximum temperatures of flames: -
Coal gas in Bunsen burner (Waggener, 1896) 1770° C.
" " " " (Berkenbusch, 1899) 1830°
" " " " (White & Traver, 1902) 1780°
" " " "
(Féry, 1905) 1871°
The following are given by Féry: -
Acetylene 2548° C.
Alcohol 1705°
Hydrogen (in air) 1900°
Oxy-hydrogen 2420°
Oxy-coal gas blowpipe 2200°
Source of Light in Flames. - We may consider first those flames where solid particles are out of the question; for example, the flame of carbon monoxide in air. The old idea that the luminosity was due to the thermal glow of the highly heated product of combustion has been challenged independently by a number of observers, and the view has been advanced that the emission of light is due to radiation attendant upon a kind of discharge of chemical energy between the reacting molecules. E. Wiedemann proposed the name "chemi-luminescence" for radiation of this kind. The fact is that colourless gases cannot be made to glow by any purely thermal heating at present available, and products of combustion heated to the average temperature of the flames in which they are produced are non-luminous. On the other hand, it must be remembered that in a mass of burning gas only a certain proportion of the molecules are engaged at one instant in the act of chemical combination, and that the energy liberated in such individual transactions, if localized momentarily as heat, would give individual molecules a unique condition of temperature far transcending that of the average, and the distribution of heat in a flame would be very different from that existing in the same mixture of gases heated from an external source to the same average temperature. The view advocated by Smithells is that in the chemical combination of gases the initial phase of the formation of the new molecule is a vibratory one, which directly furnishes light, and that the damping down of this vibration by colliding molecules is the source of that translatory motion which is evinced as heat. This, it will be seen, is an exact reversal of the older view.
The view of Sir H. Davy that "whenever a flame is remarkably brilliant and dense it may always be concluded that some solid matter is produced in it" can be no longer entertained. The flames of phosphorus in oxygen and of carbon disulphide in nitric oxide contain only gaseous products, and Frankland showed that the flames of hydrogen and carbon monoxide became highly luminous under pressure. From his experiments Frankland was led to the generalization that high luminosity of flames is associated with high density of the gases, and he does not draw a distinction in this respect between high density due to high molecular weight and high density due to the close packing of lighter molecules. The increased luminosity of a compressed flame is not difficult to understand from the kinetic theory of gases, but no explanation has appeared of the luminosity considered by Frankland to be due merely to high molecular weight. It is possible that the electron theory may ultimately afford a better understanding of these phenomena.
Structure of Flame. - The vagueness of the term structure, as applied to flames, is to be seen from the very conflicting accounts which are current as to the number of differentiated parts in different flames. Unless this term is restricted to sharp differences in appearance, there is no limit to the number of parts which may be selected for mention. The flame of carbon monoxide, when the gas is not mixed with air before it issues from the burner, shows no clearly differentiated structure, but is a shell of blue luminosity of shaded intensity - a hollow cone if the orifice of the burner be circular and the velocity of the gas not immoderate, or a double sheet of fan shape if the burner have a slit or two inclined pores which cause the jets of issuing gas to spread each other out. Such a flame has but one single distinct feature, and this is not surprising, as there is no reason to suppose that there is any difference in the chemical process or processes that are occurring in different quarters of the flame. The amount of materials undergoing this transformation in different parts of the flame may and does vary; the gases become diluted with products of combustion, and the molecular vibrations gradually die down. These things may cause a variation in the intensity of the light in different quarters, but the differences induced are not sharp or in any proper sense structural. A flame of this kind may develop a secondary feature of structure. If carbon monoxide be burnt in oxygen which is mixed or combined with another element there may be an additional chemical process that will give light; flames in air are sometimes surrounded by a faintly luminous fringe of a greenish cast, apparently associated with the combination of nitrogen with oxygen (H.B. Dixon). Carbon monoxide on being strongly heated begins to dissociate into carbon and carbon dioxide; if the unburnt carbon monoxide within a flame of that gas were so highly heated by its own burning walls as to reach the temperature of dissociation, we might expect to see a special feature of structure due to the separated carbon. Such a temperature does not, however, appear to be reached.
Apart from hydrocarbon flames not much has been published in reference to the structure of flames. The case of cyanogen is of peculiar interest. The beautiful flame of this gas consists of an almost crimson shell surrounded by a margin of bright blue. Investigations have shown that these two colours correspond to two steps in the progress of the combustion, in the first of which the carbon of the cyanogen is oxidized to carbon monoxide and in the second the carbon monoxide oxidized to carbon dioxide.
The inversion of combustion may bring new features of structure into existence; thus when a jet of cyanogen is burnt in oxygen no solid carbon can be found in the flame, but when a jet of oxygen is burnt in cyanogen solid carbon separates on the edge of the flame.
Hydrocarbon Flames. - As already stated the flames of carbon compounds and especially of hydrocarbons have been much more studied than any other kind, as is natural from their common use and practical importance. The earliest investigations were made with coal gas, vegetable oils and tallow, and the composite and complex nature of these substances led to difficulties and confusion in the interpretation of results. One such difficulty may be illustrated by the fact, often overlooked, that when a mixed gaseous combustible issues into air the individual component gases will separate spontaneously in accordance with their diffusibilities: hydrogen will thus tend to get to the outer edge of a flame and heavy hydrocarbons to lag behind.
The features of structure in a hydrocarbon flame depend of course on the manner in which the air is supplied. The extreme cases are (i.) when the issuing gas is supplied before it leaves the burner with sufficient air for complete combustion, as in the blast blowpipe, in which case we have a sheet of blue undifferentiated flame; and (ii.) when the gas has to find all the air it requires after leaving the burner. The intermediate stage is when the issuing gas is supplied before leaving the burner with a part of the air that is required. In this case a two-coned flame is produced. The general theory of such phenomena has already been discussed. It must be remarked that the transition of one kind of flame into the others can be effected gradually, and this is seen with particular ease and distinctness by burning benzene vapour admixed with gradually increasing quantities of air. The key to the explanation of the structure of an ordinary luminous flame, such as that of a candle, is to be found, according to Smithells, by observing the changes undergone by a well-aerated Bunsen flame as the "primary" air is gradually cut off by closing the air-ports at the base of the burner. It is then seen that the two cones of flame evolve or degenerate into the two recognizable blue parts of an ordinary luminous flame, whilst the appearance of the bright yellow luminous patch becomes increasingly emphasized as a hollow dome lying within the upper part of the blue sheath. There are thus three recognizable features of structure in an ordinary luminous flame, each region being as it were a mere shell and the interior of the flame filled with gas which has not yet entered into active combustion. If, as is suggested, the blue parts of an ordinary luminous flame are the relics of the two cones of a Bunsen flame, the chemistry of a Bunsen flame may be appropriately considered first. What happens chemically when a hydrocarbon is burned in a Bunsen burner? The air sent in with the gas is insufficient for complete combustion so that the inner cone of the flame may be considered as air burning in an excess of coal gas. What will be the products of this combustion? This question has been answered at different times in very different ways. There are many conceivable answers: part of the hydrocarbon might be wholly oxidized and the rest left unaltered to mix with the outside air and burn as the outer cone; on the other hand, there might be (as has been so commonly assumed) a selective oxidation in the inner cone whereby the hydrogen was fully oxidized and the carbon set free or oxidized to carbon monoxide; or again the carbon might be oxidized to carbon dioxide or monoxide and the hydrogen set free. There might of course be other intermediate kinds of action. Now it is important at this point to insist upon a distinction between what can be found by direct analysis as to the products of partial combustion, and what can be imagined or inferred as the transitory existence of substances of which the products actually found in analysis are the outcome. We shall consider only in the first instance what substances are found by analysis. Earlier experiments on the Bunsen burner in which coal gas was used, and the gases withdrawn directly from the flame by aspiration, gave no very clear results, but the introduction of the cone-separating apparatus and the use of single hydrocarbons led to more definite conclusions. The analysis of the inter-conal gases from an ethylene flame gave the following numbers: - carbon dioxide = 3.6; water = 9.5; carbon monoxide = 15.6; hydrocarbons = 1.3; hydrogen = 9.4; nitrogen = 60.6.
It appears therefore, and it may be stated as a fact, that a considerable amount of hydrogen is left unoxidized, whilst practically all the carbon is converted into monoxide or dioxide. As the gases have cooled down before analysis and as the reaction CO + H2O ⇄ CO2 + H2 is reversible, it may be objected that the inter-conal gases may have a composition when they are hot very different from what they show when cold. Experiments made to test this question have not sustained the objection. Subsequent experiments on the oxidation of hydrocarbons have made it appear undesirable to use the expression "preferential combustion" or "selective combustion" in connexion with the facts just stated; but for the purpose of describing in brief the chemistry of a hydrocarbon flame it is necessary to say that in the inner cone of a Bunsen flame hydrogen and carbon monoxide are the result of the limited oxidation, and that the combustion of these gases with the external air generates the outer cone of the flame. As to the actual stages in the limited oxidation of a hydrocarbon a large amount of very valuable work has been carried out by W.A. Bone and his collaborators. Different hydrocarbons mixed with oxygen have been circulated continuously through a vessel heated to various temperatures, beginning with that (about 250° C.) at which the rate of oxidation is easily appreciable. Proceeding in this way, Bone, without effecting a complete transformation of the hydrocarbon into partially oxidized substances, has isolated large quantities of such products, and concludes that the oxidation of a hydrocarbon involves nothing in the nature of a selective or preferential oxidation of either the hydrogen or the carbon. He maintains that it occurs in several well-defined stages during which oxygen enters into and is incorporated with the hydrocarbon molecule, forming oxygenated intermediate products among which are alcohols and aldehydes. The reactions between ethane and ethylene with an equal volume of oxygen would be represented as follows: -
The affinity between the hydrocarbon and oxygen at a high temperature is so great that, when the supply of oxygen is sufficient to carry the oxidation as far as the second stage, practically no decomposition of the monohydroxy molecule formed in the first stage occurs. This is especially the case with unsaturated hydrocarbons.
As a crucial test decisive against the hypothesis of preferential carbon oxidation, Bone cites the experiment of firing a mixture of equal volumes of ethane and oxygen sealed up in a glass bulb. In such a case a lurid flame fills the vessel, accompanied by a black cloud of carbon particles and considerable condensation of water. About 10% of methane is also found. It is impossible within the limits of this article to give a more extended account of these later researches on the oxidation of hydrocarbons. They make it evident that the relative oxidizability of carbon and hydrogen cannot form the basis of a general theory of the combustion of hydrocarbons, and that both the a priori view that hydrogen is the more oxidizable element, and the inference from the behaviour of ethylene when exploded with its own volume of oxygen, viz. that carbon is the more oxidizable element in hydrocarbons, are not in harmony with experimental facts.
The view that the bright luminosity of hydrocarbon flames is due "to the deposition of solid charcoal" was first put forward by Sir Humphry Davy in 1816. In explaining the origin of this charcoal, Davy used somewhat ambiguous language, stating that it "might be owing to a decomposition of a part of the gas towards the interior of the flame where the air was in smallest quantity." This statement was interpreted commonly as implying that the charcoal became free by the preferential combustion of the hydrogen, and such an interpretation was given explicitly by Faraday. Whatever may have been Davy's view with regard to this part of the theory, his conclusion that finely divided carbon was the cause of luminosity in hydrocarbon flames was not questioned until 1867, when E. Frankland, in connexion with researches already alluded to, maintained that the luminosity of such flames was not due in any important degree to solid particles of carbon, but to the incandescence of dense hydrocarbon vapours. Among the arguments adduced against this view the most decisive is furnished by the optical test first used by J.L. Soret. If the image of the Sun be focussed upon the glowing part of a hydrocarbon flame the scattered light is found to be polarized, and it is indisputable that the luminous region is pervaded by a cloud of finely divided solid matter. The quantity of this solid (estimated by H.H.C. Bunte to be 0.1 milligram in a coal-gas flame burning 5 cub. ft. per hour) is sufficient to account for the luminosity, so that Davy's original view may be said to be now universally accepted.
The remaining question with regard to the luminosity of a hydrocarbon flame relates to the manner in which the carbon is set free. The fact-that hydrocarbons when strongly heated in absence of air will deposit carbon has long been known and is daily evident in the operation of coal-gas making, when gas carbon accumulates as a hard deposit in the highly-heated crown of the retorts. There is no difficulty in supposing therefore that the carbon in a flame is separated from the hydrocarbon within it by the purely thermal action of the blue burning walls of the flame. Many experiments might be adduced to confirm this view. It is sufficient to name two. If a ring of metal wire be so disposed in a small flame as to make a girdle within the blue walls towards the base, the withdrawal of heat is rapid enough to prevent the maintenance of a temperature sufficient to cause a separation of carbon, and the bright luminosity disappears. Again, if the flame of a Bunsen burner be fed through the air-ports not with air but with some neutral gas such as nitrogen, carbon dioxide or steam, the dilution of the burning gas and the hydrocarbon within it becomes so great that the temperature of separation is not attained, no carbon is separated and the flame consists of a single blue shell.
Whilst it is thus easy to understand generally why carbon becomes separated as a solid within a flame, it is not easy to trace the processes by which the carbon becomes separated in the case of a given hydrocarbon. According to M.P.E. Berthelot, who made prolonged and elaborate researches on the pyrogenetic relationships of hydrocarbons, these compounds only liberate carbon by a process of the continual coalescence of hydrocarbon molecules with the elimination of hydrogen, until there is left the limiting solid hydrocarbon hardly distinguishable from carbon itself and constituting the glowing soot of flames.
V.B. Lewes, on the other hand, basing his conclusions on a study of the thermal decomposition of hydrocarbons, on temperature measurements of flames and analysis of their gases, has more recently developed a theory of flame luminosity in which the formation and sudden exothermic decomposition of acetylene are regarded as the essential incidents productive of carbon separation and luminosity. Smithells has disputed the evidence on which this theory is based and it appears to have gained no adherence from those who have worked in the same field; but as it has not been formally disavowed by the author and has found its way into some text-books, it is mentioned here.
W.A. Bone and H.F. Coward (Journ. Chem. Soc., 1908) published the results of a very careful study of the decomposition of hydrocarbons when heated in a stationary condition and when continually circulated through hot vessels. Their results disclose once more the great difficulty of tracing the processes of decomposition and of arriving at a generalization of wide applicability, but they appear to be conclusive against the views both of Berthelot and of Lewes.
They do not think that the decomposition of hydrocarbons can be adequately represented by ordinary chemical equations owing to the complexity of the changes which really take place. Methane, which is the most stable of the hydrocarbons, appears to be resolved at high temperatures directly into carbon and hydrogen, but the phenomenon is dependent mainly on surface action; ethane, ethylene and acetylene undergo decomposition throughout the body of the gas (loc. cit. p. 1197 et seq.).
"In the cases of ethane and ethylene it may be supposed that the primary effect of high temperature is to cause an elimination of hydrogen with a simultaneous loosening or dissolution of the bond between the carbon atoms, giving rise to (in the event of dissolution) residues such as : CH2 and ∶ CH. These residues, which can only have a very fugitive separate existence, may either (a) form H2C : CH2 and HC ∶ CH, as the result of encounters with other similar residues, or (b) break down directly into carbon and hydrogen, or (c) be directly hydrogenized to methane in an atmosphere rich in hydrogen. These three possibilities may all be realized simultaneously in the same decomposing gas in proportions dependent on the temperature, pressure and amount of hydrogen present. The whole process may be represented by the following scheme, the dotted line indicating the tendency to dissolve a bond between the carbon atoms which becomes actually effective at higher temperatures: -
"In the ease of acetylene, the main primary change may be either one of polymerization or of dissolution according to the temperature, and if the latter, it may be supposed that the molecule breaks down across the triple bond between the carbon atoms, giving rise to 2(∶ CH), and that these residues are subsequently either resolved into carbon and hydrogen or "hydrogenized" according to circumstances, thus: -
"Acetylene is, moreover, distinguished by its power of polymerization at moderate temperatures so that whether it is the gas initially heated or whether it is a prominent product of the decomposition of another hydrocarbon polymerization will occur to an extent dependent on temperature."
We may describe briefly the view to which we are led as to the genesis of an ordinary luminous hydrocarbon flame: -
The gaseous hydrocarbon issues from the burner or wick, let us suppose, in a cylindrical column. This column is not sharply marked off from the air but is so penetrated by it that we must suppose a gradual transition from the pure hydrocarbon in the centre of column to the pure air on the outside. Let us take a thin transverse slice of the flame, near the lower part of the wick or close to the burner tube. At what lateral distance from the centre will combustion begin? Clearly, where enough oxygen has penetrated the column to give such partial combustion as takes place in the inner cone of a Bunsen burner. This then defines the blue region. Outside this the combustion of the carbon monoxide, hydrogen and any hydrocarbons which pass from the blue region takes place in a faintly luminous fringe. These two layers form a sheath of active combustion, surrounding and intensely heating the enclosed hydrocarbons in the middle of the column. These heated hydrocarbons rise and are heated to a higher temperature as they ascend. They are accordingly decomposed with separation of carbon in the higher parts of the flame, giving the region of bright yellow luminosity. There remains a central core in which neither is there any oxygen for combustion nor a sufficiently high temperature to cause carbon separation. This constitutes the dark interior region of the flame. We thus account for the different parts of the flame. It is to be noted, however, that the bright blue layer only surrounds the lower part of the flame, whilst the pale, faintly-luminous fringe surrounds the whole flame. The flame also is conical and not cylindrical. The foregoing explanation is therefore not quite complete. Let us suppose that the changes have gone on in the small section of the flame exactly as described and consider how the processes will differ in parts above this section. The central core of unburned gases will pass upwards and we may treat it as a new cylindrical column which will undergo changes just as the original one, leaving, however, a smaller core of unburned gases, or, in other words, each succeeding section of the flame will be of smaller diameter. This gives us the conical form of the flame. Again, the higher we ascend the flame the greater proportionally is the amount of separated carbon, for we have not only the heat of laterally outlying combustion to effect decomposition, but also that of the lower parts of the flame. The lower part of a luminous flame accordingly contains less separated carbon than the upper. Where the hydrocarbon is largely decomposed before combustion we have no longer the conditions of the Bunsen flame, and so in the upper parts of a luminous flame the bright blue part fades away. The luminous fringe would, however, be continued, for the separated hydrogen has still to burn. In this way then we may reasonably account for the existence, position and relative sizes of the four regions of an ordinary luminous flame.
(A. S.)
Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)
