Popular Science Monthly/Volume 63/July 1903/Why a Flame Emits Light - the Development of the Theory
|WHY A FLAME EMITS LIGHT—THE DEVELOPMENT OF THE THEORY.|
BY Professor ROBERT MONTGOMERY BIRD, Ph.D.,
UNIVERSITY OF THE STATE OF MISSOURI.
AS one would naturally suppose, the theory now generally held regarding the nature of an ordinary flame and its power to emit light is not altogether the result of modern research, but one which has been evolved from very ancient and hazy notions. Naught else is to be expected when we consider the important place fire has held throughout the development of mankind. It is the first recorded object of his worship, and we have reason to believe that all architecture had its beginning in rude structures erected to protect the sacred fire. It is not the nature of man to see phenomena so striking as those which attend the consumption of matter by fire and not speculate upon them. But the centuries had multiplied and modern times had been reached before man's ideas regarding fire, flame and light became distinct, and the use of these terms differentiated. The best text-books and works on natural philosophy published near the end of the eighteenth century still used the terms with great looseness, and the conceptions of the material nature of flame and light were yet in their death struggles.
After the corpuscular theory of light had given place to the wave theory, conflicting ideas arose as to why and how a flame emits light waves. When it was agreed that the waves were sent out by solid particles of carbon heated to incandescence, the question of the origin of the carbon, or the chemical changes taking place in the flame, was discussed, and along with this the source of heat which renders it incandescent. The last and most generally accepted answer to these two questions—the origin of carbon particles and the source of heat—is given in the 'acetylene theory,' first advanced in 1892 by Professor Vivian B. Lewes, of England.
This theory expressed briefly is that a portion of the hydrocarbon gas, by the heat of combustion of another portion, is converted into acetylene, and that this on being decomposed by heat furnishes the carbon particles, which particles are rendered incandescent mainly by the heat liberated when the gas is decomposed; acetylene being a substance which absorbs heat during its formation and hence liberates heat when it breaks down. Whatever is burned, whether a solid candle or liquid oil, must pass through the gaseous state, and hence this applies to all flames used for lighting purposes.
But before explaining this theory more fully and seeing upon what experimental evidence it is based, it would be well to consider its genesis and briefly recall the ancient notions regarding 'artificial' light.
Light was first confused with seeing, and it is said that up to the time of Aristotle men commonly thought they saw by reason of something shooting out from the eyes and coming in contact with objects; the converse of the Cartesian conception of many centuries later, that certain movements in bodies cause them to shoot out minute particles in all directions, which, striking the eye or causing 'globules' of air to strike it, excite vision.
The fluid nature of fire and the corporeal nature of light, which were believed in throughout the early and middle ages, seem to have been first doubted by Sir Francis Bacon about the end of the sixteenth century, although he was by no means sure that these conceptions were wrong. Bacon classed together the light from flames, decayed wood, glowworms, silks, polished surfaces, etc., and said that inasmuch as some animals can see in the dark, air has some light of itself. Boerhaave, somewhat later, also expressed doubts as to the substantive nature of fire.
Among the first recorded experiments upon the nature and action of luminous flames are those which were carried out by Sir Robert Boyle between 1660 and 1670. He attempted to prove by experiment whether the light from a flame is like that from the sun, and whether it is corporeal or merely a quality. He allowed a flame to play on metals directly and also when in open and sealed vessels, and because the substance formed a calx and gained in weight, he thought that the light or flame (he uses the terms indiscriminately) had combined with the metal, and hence it must be a fluid. Boyle also conducted a large number of experiments upon live or 'quick' coals, phosphorescent bodies, animals and insects to see the effect of exhausting a receiver in which they were placed, and he seems to have concluded that the lights from live coals, rotten wood and putrefying fish differ not in kind but only in degree. He considered that the increase of light from coals, etc., and the reviving of certain insects when air was readmitted to the receiver indicated a relation between a visible flame and the so-called 'vital flame.' But he would not commit himself upon the question of the supposed kinship between the 'flame' from live coals and rotten wood and the 'vital flame' thought to be burning in the hearts of all living beings.
The interesting views of Sir Isaac Newton are set forth in a number of queries published in his work entitled 'Optics.' As is well known, Newton believed in the material nature of light, and he asserted that the change of light into matter and of matter into light is an acknowledged possibility and of common occurrence. He attributed the light which appears when a body is rapidly and repeatedly struck or when heated beyond a certain point, as when flint and steel are struck together, etc., to vibrations of the parts of the body so rapid as to throw off the particles which, according to Newton's idea, occasion the sensation of light. With these he also classed electric sparks, saying that the 'electric vapor' excited by rubbing glass dashes against a strip of paper or the end of the finger held to it, is thereby so agitated as to cause it to emit light. He thought the light from glowworms and putrefying matter was of the same kind as the above, and said that the light seen at night in the eyes of certain animals, cats for instance, is 'due to vital motions.'
Regarding true luminous flames Newton's ideas were nearer those of the present time. He wrote "Is not fire a body heated so hot as to emit light copiously? For what else is a red hot iron than fire? And what else is a burning coal than red hot wood?" "Is not flame a vapor, fume or exhalation heated red hot, that is, so hot as to shine? For bodies do not flame without emitting a copious fume, and this fume burns in the flame. Metals in fusion do not flame for want of a copious fume." "All fuming bodies, as oil, tallow, wax, wood, etc., by fuming waste and vanish into burning smoke." 'Put out the flame and the smoke is visible, it often smells; and the nature of the smoke determines the color of the flame.' "Smoke passing through flame can not but grow red hot, and red hot smoke can have no other appearance than that of flame."
During the hundred years, more or less, following the publication of Newton's views there was little change in the prevailing theories. Stahl said 'flame is light' liberated from bodies in the act of combustion, and that light and heat are the constant attendants of flre; fire combined with combustible matter was 'phlogiston.' Scheele said light, heat and fire are combinations of air and 'phlogiston.' Lavoisier thought flame to be light disengaged from air, with which it had been in combination, and this idea seems to have been adopted by most of the French chemists.
There might be mentioned in this connection the queer ideas regarding our being able to see objects, and the emission of light by incombustible bodies, which were held during the latter half of the eighteenth century. As expressed by Macquer, and quoted by Fourcroy, "The vibrations (under the impulse of more or less heat) dispose the particles (of bodies) in such a manner that their faces, acting like so many little mirrors, reflect upon our eyes the rays of light which are in the air by night as well as by day; for we are involved in darkness during the night for no other reason but because they are not then so directed as to face our organs of sight."
At a single step we pass from the rather crude ideas of the older thinkers to those ideas which obtain at the present day, and the transition finds little expression in the literature.
About the year 1816 Sir Humphry Davy advanced what has been known ever since as the 'solid particle' theory of luminosity; a theory which went unchallenged for forty-five years and was accepted by practically every one.
He was experimenting upon the combustion taking place in his famous safety lamp and said, "I was led to imagine that the cause of the superiority of the light of a stream of coal gas might be owing to the decomposition of a part of the gas towards the interior of the flame, where the air is in smallest quantity, and the deposition of solid charcoal, which, first by its ignition and afterwards by its combustion, increased to a high degree the intensity of the light; and a few experiments soon convinced me that this was the true solution of the problem. "Whenever a flame is remarkably brilliant and dense, it may always be concluded that some solid matter is produced in it; on the contrary, whenever a flame is extremely feeble and transparent it may be inferred that no solid matter is formed." The idea that solid carbon in the flame is the source of its light was not original with Davy—he says it was suggested by a Mr. Hare—but it was Davy's investigations which put it on a firm basis and he formulated the theory.
Davy showed the relation between the heat and light of flames, the effects of rarefaction and compression of the surrounding air and the influence of cooling and heating. He pointed out also that a luminous flame will deposit carbon on a cold surface, and if rendered non-luminous no carbon can be obtained. These conclusions were immediately accepted and were not seriously disputed until the appearance in 1861 of a communication to the Royal Society from E. Frankland.
In this article Frankland advanced what has come to be known as the 'dense vapor' theory. He and his adherents claimed that, although solid particles in a flame do cause it to emit light, the light from our ordinary illuminating flames is dependent to a great extent upon the presence of dense, transparent, hydrocarbon vapors from which it is radiated, and is not due to the presence of incandescent solid carbon particles. They further claimed that the soot deposited is not carbon, but a mixture of dense hydrocarbons of remarkably high boiling points.
Frankland was led to take up his investigations by seeing a report that candles burned at the same rate on the top of Mt. Blanc as in the valley at its foot; and a second report regarding the retardation of the bursting of shells with time fuses at high elevations in India.
Besides carrying on investigations in warm in the meantime by the fire of his enthusiasm. Many interesting facts were brought to light by these investigations, but his use of them in interpreting the causes of luminosity in ordinary flames led him into error, and, although he found adherents at the time, his views have long since been replaced by those based upon more careful observation. The importance of the work of Frankland lay not so much in what he did as in what he led others to do; and since the publication of his views a great deal has been done by Heumann, Stein, Smithells, Burch, Lewes and others.rarefied air in his laboratory, he climbed to the top of Mt. Blanc with a goodly supply of standard candles and timed their slow wasting away; probably keeping
Stein disproved Frankland's assertion that soot is a mixture of dense hydrocarbons by showing that it can not be volatilized even by great heat, and that it contains only about nine tenths of one per cent, of hydrogen, which can be separated from it only at high temperatures in an atmosphere of chlorine.
Nor did Frankland's view that glowing, dense vapors cause the light appeal to Heumann, who thought it unlikely that such dense vapors exist in a flame or that there is a sufficiently high temperature to cause them to glow. He knew, of course, that at a temperature like that of an electric arc many gases do glow and give continuous spectra, and that a highly heated gas under pressure acts likewise; but he argued that if carbon really does exist as such in a flame, it most probably is the source of luminosity. To prove its presence or absence he studied the effects upon a flame of heating and cooling it, of diluting and varying the temperature of the gases supplied to it, its transparency and the shadows cast by it, as well as other phenomena; and the results of his experiments led him to give unqualified support to the theory of Davy.
Some account of the salient features at least of Heumann's elaborate investigation must be given in order to convey any idea of his part in firmly fixing the 'solid particle' theory. By allowing a luminous flame to play upon a surface which rapidly conducted heat away from it, like a platinum dish, its luminosity was destroyed. Heating the upper surface of the dish restored the luminosity, and hence Heumann concluded that cooling a flame diminishes its light-giving properties, while heating increases them. He varied the temperature of illuminating gas before it reached the burner and found that the same effects were produced. The heating in some cases increased the normal light-giving power as much as a hundred and twenty-five per cent. Further investigation showed that luminosity can also be diminished or destroyed by rapid oxidation of the hydrocarbons, as well as by diluting them with a neutral gas like nitrogen or carbon dioxide; the effect of dilution being to necessitate a higher temperature for luminosity. He next rendered a flame non-luminous by cooling, introduced chlorine into it to break down the hydrocarbons, and obtained a brilliant light. A porcelain rod introduced into the lower part of a flame cooled it and decreased its light, but collected no carbon, while, if introduced into the upper part, its under side became coated with soot. Heumann argued that if Frankland was right and the light is reflected from dense hydrocarbon vapors, these should be condensed on all sides of the rod at once in a quiet flame, while, as a matter of fact, soot was deposited only on the under side; and furthermore, soot can also be collected upon a surface too hot to condense hydrocarbons at all. He therefore concluded that the surface merely stops carbon which is formed lower down in the flame. If one luminous flame is allowed to play against another, the carbon is rolled up and can be seen as glowing particles in the outer non-luminous sheath.
Frankland had said that flames can not contain solid particles because they are transparent. Heumann pointed out that thick flames are opaque and that thin ones are no more transparent than is an equal layer of soot rising from burning turpentine; the rapidity of the motion of the particles preventing any obstruction to the view, just as is the case with a rapidly revolving, spoked wheel.
Heumann next took up the phenomena of shadows and showed that the luminous portion casts a definite shadow when interposed between sunlight and a screen, and that the shadow is continuous for a luminous turpentine flame and the column of soot above it. And further, that a hydrogen flame which ordinarily casts no shadow and gives no light will cast a sharp shadow and emit a fairly bright light if passed through suspended lampblack or if it sweeps any solid matter into the flame. Luminous vapors do not cast shadows, absorption bands being very different from true shadows.
C. J. Burch found that when sunlight is reflected from a luminous flame it is polarized, while if reflected by glowing vapors, however dense, it does not exhibit this phenomenon. Sunlight which was reflected and refracted by luminous flames was found to exhibit phenomena identical with that reflected and refracted by non-luminous flames rendered luminous by the introduction of solid matter, and also with light reflected, and refracted by very finely divided solid matter held in suspension in a liquid. The phenomena presented by like experiments with glowing vapors were totally different. All of Burch 's work was confirmed by Stokes some years later.
There was now left no shadow of doubt about carbon being the source of the light rays, and the next question that concerned investigators was the chemical changes which give rise to carbon particles.
Sir Humphry Davy thought the separation of carbon to be due to a decomposition of the hydrocarbon compounds (of which all illuminants are composed) within the flame where the air is in smallest quantity, and no other cause was assigned by other investigators. Prior to 1861 the view, it seems, was that carbon is liberated because of a supposed greater affinity of oxygen for the hydrogen of the hydrocarbon than for the carbon, there not being enough for both. But these points had to be tested.
In the study of the chemical changes that take place, a flame burning at a circular orifice offered the best conditions. As explained in text-books of chemistry, such a flame may be thought of as being made up of an inner, faintly luminous cone fitting into an outer, brightly luminous one—as a finger fits into a glove finger—this latter being surrounded by a non-luminous sheath of water vapor and carbon dioxide. It was desirable to separate these two cones, in order to study the gas after it had left the inner cone and before any change had been brought about by the conditions existing in the outer cone. This separation was first accomplished by Techlu, in France, and Arthur Smithells, in England, working independently, with a piece of apparatus, the essential features of which are pictured in cross-section in Fig. 1. By a proper control of the relative proportions of gas and air the inner cone was made to burn at the orifice i, while the outer cone burned at the orifice o. The outer cone got its oxygen from the surrounding air, while that for the lower flame was supplied along with the gas. The temperature of each cone was measured and the gases entering and leaving each were analyzed. It was found that as the proportion of gas to air was increased, the tip of the inner or lower cone became brightly luminous and a column of soot passed upward through the tube, becoming faintly luminous in the outer edge of the upper flame. As soon as the inner cone becomes luminous the unsaturated hydrocarbon compound known as acetylene begins to appear among the gases passing to the outer cone.
Vivian B. Lewes now attacked the problem as to how carbon comes to be in the flame in the free state. He analyzed gas drawn from different parts of a coal-gas flame, measured the temperature of its different parts, etc., publishing his results between 1893 and 1895. These results may be stated as follows: Coal-gas consists mainly of a mixture of hydrogen and hydrocarbons, both saturated and unsaturated. In an ordinary 'fishtail' burner flame all hydrogen is consumed before the middle of the luminous portion is reached. Of the saturated hydrocarbons about seventy-five per cent, disappears as such in the dark portion and about twenty-four per cent, is lost in the lower half of the luminous part. In the dark part there occurs a transformation of saturated into unsaturated hydrocarbons, along with a general breaking down of all to yield products less rich in hydrogen and the oxides of carbon. At the point where luminosity just begins, seventy to eighty per cent, of the unsaturated compounds is acetylene, although less than one per cent, was originally present. No acetylene could be found in the flame when it was made non-luminous.
By causing pure gases to pass through tubes heated to known temperatures and analyzing the products formed, Lewes studied the effects of heat upon both saturated and unsaturated hydrocarbons. At 800° C. an unsaturated compound, like ethylene, C2H4, breaks down into hydrogen and the still more unsaturated acetylene, C2H2. At 1200° C. the very stable, saturated hydrocarbons decompose into acetylene and hydrogen, and the acetylene in turn decomposes into carbon and hydrogen. Even very dense hydrocarbons decompose at 1200° C. These results strengthened Lewes 's conviction that under the baking action of the flame-walls in the lower portions acetylene is produced in relatively large quantities and that this is the source of the carbon.
The question which immediately presented itself was. Does there exist in an ordinary flame such conditions of temperature as may bring about the formation of acetylene from the very stable constituents of the illuminants? On measuring the temperatures at various places the necessary temperatures were found to exist.
The work was complete and conclusive and forced a general acceptance of the theory that acetylene is the immediate source of the carbon.
But a yet harder problem presented itself. What gives rise to heat sufficient to make the carbon become incandescent?; a burning question certainly and one not easy to answer.
From the time of Davy to the year 1892 the only opinion was that the burning hydrogen, carbon monoxide and hydrocarbons furnished the heat necessary to raise carbon to incandescence. In that year Lewes advanced his 'latent heat' theory. This theory declared that the latent heat set free when acetylene is decomposed instantly heats the carbon particles thus set free to incandescence.
After showing that the heat of combustion of a flame is only sufficient to render carbon faintly luminous, Lewes compared the temperatures of flames burning coal-gas, the unsaturated hydrocarbon gas, ethylene, and the still less saturated acetylene, and also the amount of light given by each when burning equal volumes of gas per hour from burners best suited to each. He likewise studied the temperatures developed when acetylene is exploded and the localization of the heat set free by its decomposition. His experiments were ingenious and convincing. By comparing ethylene, C2H4, with acetylene, C2H2 (where for equal consumption the same number of carbon atoms were present), and also with coal-gas, it was seen that the luminous portion of the acetylene, flame is not as hot as that of either ethylene or coal-gas, while the illuminating powers of the flames were: acetylene, 240.0 candle power, ethylene, 65.5 c.p. and coal-gas, 16.8 c.p. Evidently the heat of combustion does not account for the incandescence of the carbon; for if it did the cooler acetylene flame would give less light, while, as a matter of fact, it gives twice as much as the ethylene and about fourteen times as much light as the very much hotter coal-gas flame. It was evident that our temperature measuring instruments do not detect the heat of the carbon particles themselves.
To see if luminosity be even partly due to the latent heat of acetylene, Lewes exploded that gas in a closed tube. This was done by wrapping a bit of fulminate of mercury in tissue paper and suspending it by copper wires joined by platinum in contact with the fulminate, and passing an electric current. There followed a brilliant flash of light and a complete decomposition of the gas, and of the eudiometer as
well. Pieces of glass were coated with carbon, and the tissue paper was not scorched except in a small hole where the explosion of the fulminate had burst through. This experiment showed the formation of carbon, the emission of a brilliant light and the localization of the heat liberated. But as the decomposition in a flame can hardly be as rapid as in this experiment, and as hydrogen and oxygen also give a feeble light when exploded, he sought to detect the rise in temperature at the moment of decomposition when this is caused by heat. He arranged a thermo-couple in a small tube so that only the turn of wires was exposed, and after sweeping out the air passed a slow current of acetylene through the tube, the arrangement being as shown in Fig. 3. The heat was raised throughout the tube at a rate of about 10° C. per minute, and almost as soon as the temperature of area a passed 800° C. it took a sudden leap to 1000° C, the gas burst into a lurid flame and streams of carbon passed on through the tube. Although the temperature of area h was made considerably higher than a the carbon passing through it was not luminous. This experiment would seem to leave no doubt that the incandescence is caused by latent heat, yet further evidence was produced. In another experiment in which diluted acetylene was used it required a higher heat to cause the decomposition and luminosity. This latter is the condition existing in a flame, and the temperature there found is above that required. In other experiments it was found that if the flame temperature were high enough the luminosity was directly proportional to the amount of acetylene in the flame at the point where luminosity generally begins. Acetylene was introduced at the corresponding place in a non-luminous flame through very fine holes in a small capillary platinum tube, and the rate of its flow, as well as that of the illuminating gas, was measured and controlled so as to have present the amount of acetylene, which analysis showed to exist in a similar luminous flame. At the holes there was an intense light, and dull red streams of carbon passed upward in the flame.
Lewes sums up his conclusions, drawn from all his work, about as follows: When the hydrocarbon gas leaves the jet at which it is burned, those portions which come in contact with the air are consumed and form a wall of flame, which surrounds the issuing gases. The unburnt gas in its passage through the lower heated area undergoes a number of chemical changes, brought about by the heat radiated from the flame walls; the principal change being the conversion of hydrocarbons into acetylene, hydrogen and methane. The temperature of the flame rapidly increases with the distance from the jet and reaches a point at which it is high enough to decompose acetylene into carbon and hydrogen with a rapidity almost that of an explosion. The latent heat so suddenly set free is localized by the proximity of carbon particles, which by absorbing it become incandescent and emit the larger part of the light given out by the flame; although the heat of combustion causes them to glow somewhat until they come into contact with oxygen and are consumed. This external heating gives rise to little of the light.
There have been opponents to this theory of the cause of luminosity—as there are, fortunately, of all theories—but the evidence is so strong and covers so many points, and so many investigators have confirmed one part or another of the work, that it has been generally accepted as a true statement of the facts with which it deals.
- Fourcroy's 'Chemistry,' press date 1796.
- The terms 'saturated' and 'unsaturated' have reference, among other things, to the relative quantity of hydrogen to carbon in the molecule, an unsaturated compound having relatively less hydrogen than a saturated one.