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Physical Basis Of Solar Chemistry

( Originally Published 1905 )

OMITTING all preface, attention was first drawn to an experimental arrangement intended to prove that gaseous bodies radiate heat in different degrees. Near a double screen of polished tin was placed an ordinary ring gas-burner, and on this was placed a hot copper ball, from which a column of heated air ascended. Behind the screen, but so situated that no ray from the ball could reach the instrument, was an excellent thermoelectric pile, connected by wires with a very delicate galvanometer. The pile was known to be an instrument whereby heat is applied to the generation of electric cur-rents; the strength of the current being an accurate measure of the quantity of the heat. As long as both faces of the pile are at the same temperature, no current is produced; but the slightest difference in the temperature of the two faces at once declares itself by the production of a current, which, when carried through the galvanometer, indicates by the deflection of the needle both its strength and its direction.

The two faces of the pile were in the first instance brought to the same temperature; the equilibrium being shown by the needle of the galvanometer standing at zero.

The rays emitted by the current of hot air already referred to were permitted to fall upon one of the faces of the pile; and an extremely slight movement of the needle showed that the radiation from the hot air, though sensible, was extremely feeble. Connected with the ring-burner was a holder containing oxygen gas; and by- turning a cock, a stream of this gas was permitted to issue from the burner, strike the copper ball, and ascend in a heated column in front of the pile. The result was, that oxygen showed itself, as a radiator of heat, to be quite as feeble as atmospheric air.

A second holder containing olefiant gas was then connected with the ring-burner. Oxygen and air had already flowed over the ball and cooled it in some degree. Hence the olefiant gas labored under a disadvantage. But on permitting the gas to rise from the ball, it cast an amount of heat against the adjacent face of the pile sufficient to impel the needle of the galvanometer almost to 90°. This experiment proved the vast difference between two equally invisible gases with regard to their power of emitting radiant heat.

The converse experiment was now performed. The thermo-electric pile was removed and placed between two cubes filled with water kept in a state of constant ebullition; and it was so arranged that the quantities of heat falling from the cubes on the opposite faces of the pile were exactly equal, thus neutralizing each other. The needle of the galvanometer being at zero, a sheet of oxygen gas was caused to issue from a slit between one of the cubes and the adjacent face of the pile. - If this sheet of gas possessed any sensible power of intercepting the thermal rays from the cube, one face of the pile being deprived of the heat thus intercepted, a difference of temperature between its two faces would instantly set in, and the result would be declared by the. galvanometer. The quantity absorbed by the oxygen under those circumstances was too feeble to affect the galvanometer; the gas, in fact, proved perfectly transparent to the rays of heat. It had but a feeble power of radiation: it had an equally feeble power of absorption.

The pile remaining in its position, a sheet of olefiant gas was caused to issue from the same slit as that through which the oxygen had passed. No one present could see the gas; it was quite invisible, the light went through it as freely as through oxygen or air; but its effect upon the thermal rays emanating from the cube was what might be expected from a sheet of metal. A quantity so large was cut off that the needle of the galvanometer, promptly quitting the zero line, moved with energy to its stops. Thus the olefiant gas, so light and clear and pervious to luminous rays, was proved to be a most potent destroyer of the rays emanating from an obscure source. The reciprocity of action established in the case of oxygen comes out here; the good radiator is found by this experiment to be the good absorber.

This result, now exhibited before a public audience for the first time, was typical of what had been obtained with gases generally. Going through the entire list of gases and vapors in this way, we find radiation and absorption to be as rigidly associated as positive and negative in electricity, or as north and south polarity in magnetism. So that if we make the number which expresses the absorptive power the numerator of a fraction, and that which expresses its radiative power the denominator, the result would be, that on account of the numerator and denominator varying in the same proportion, the value of that fraction would always remain the same, whatever might be the gas or vapor experimented with.

But why should this reciprocity exist? What is the meaning of absorption? what is the meaning of radiation ? When you cast a stone into still water, rings of waves surround the place where it falls; motion is radiated on all sides from the centre of disturbance. When a hammer strikes a bell, the latter vibrates; and sound, which is nothing more than an undulatory motion .of the air, is radiated in all directions. Modern philosophy reduces light and heat to the same mechanical category. A luminous body is one with its atoms in a state of vibration; a hot body is one with its atoms also vibrating, but at a rate which is incompetent to excite the sense of vision; and, as a sounding body has the air around it, through which it propagates its vibrations, so also the luminous or heated body has a medium, called ether, which accepts its motions and carries them forward with inconceivable velocity. Radiation, then, as regards both light and heat, is the transference of motion from the vibrating body to the ether in which it swings: and, as in the case of sound, the motion imparted to the air is soon transferred to surrounding objects, against which the aerial undulations strike, the sound being, in technical language, absorbed; so also with regard to light and heat, absorption consists in the transference of motion from the agitated ether to the molecules of the absorbing body.

The simple atoms are found to be bad radiators; the compound atoms good ones: and the higher the degree of complexity in the atomic grouping, the more potent, as a general rule, is the radiation and absorption. Let us get definite ideas here, however gross, and purify them after-ward by the process of abstraction. Imagine our simple atoms swinging like single spheres in the ether; they cannot create the swell which a group of them united to form a system can produce. An oar runs freely edgewise through the water, and imparts far less of its motion to the water than when its broad, flat side is brought to bear upon it. In our present language the oar,. broad side vertical, is a good radiator; broad side horizontal, it is a bad radiator. Conversely the waves of water, impinging upon the flat face of the oar-blade, will impart a greater amount of motion to it than when impinging upon the edge. In the position in which the oar radiates well, it also absorbs well. Simple atoms glide through the ether without much resistance; compound ones encounter resistance, and hence yield up more speedily their motion to the ether. Mix oxygen and nitrogen mechanically, they absorb and radiate a certain amount of heat. Cause these gases to combine chemically and form nitrous oxide, both the absorption and radiation are thereby augmented hundreds of times !

In this way we look with the telescope of the intellect into atomic systems, and obtain a conception of processes which the eye of sense can never reach. But gases and vapors possess a power of choice as to the rays which they absorb. They single out certain groups of rays for destruction, and allow other groups to pass unharmed. This is best illustrated by a famous experiment of Sir David Brewster's, modified to suit present requirements. Into a glass cylinder, with its ends stopped by disks of plate-glass, a small quantity of nitrous acid gas is introduced; the presence of the gas being indicated by its rich brown color. The beam from an electric lamp being sent through two prisms of bisulphide of carbon, a spectrum seven feet long and eighteen inches wide is cast upon the screen. Introducing the cylinder containing the nitrous acid into the path of the beam as it issues from the lamp, the splendid and continuous spectrum becomes instantly furrowed by numerous dark bands, the rays answering to which are intercepted by the nitric gas, while the light which falls upon the intervening spaces is permitted to pass with comparative impunity.

Here also the principle of reciprocity, as regards radiation and absorption, holds good; and could we, without otherwise altering its physical character, render that nitrous gas luminous, we should find that the very rays which it absorbs are precisely those which it would emit. When atmospheric air and other gases are brought to a state .of intense incandescence by the passage of an electric spark, the spectra which we obtain from them consist of a series of bright bands. But such spectra are produced with the greatest brilliancy when, instead of ordinary gases, we make use of metals heated so highly as to volatilize them. This is easily done by the voltaic cur-rent. A capsule of carbon filled with mercury, which formed the positive electrode of the electric lamp, has a carbon point brought down upon it. On separating the one from the other, a brilliant arc containing the mercury in a volatilized condition passes between them. The spectrum of this arc is not continuous like that of the solid carbon points, but consists of a series of vivid bands, each corresponding in color to that particular portion of the spectrum to which its rays belong. Copper gives its system of bands; zinc gives its system; and brass, which is an alloy of copper and zinc, gives a spectrum made up of the bands belonging to both metals.

Not only, however, when metals are united like zinc and copper to form an alloy is it possible to obtain the bands which belong to them. No matter how we may disguise the metal—allowing it to unite with oxygen to form an oxide, and this again with an acid to form a salt; if the heat applied be sufficiently intense, the bands belonging to the metal reveal themselves with perfect definition. Into holes drilled in a cylinder of retort carbon, pure culinary salt is introduced. When the carbon is made the positive electrode of the lamp, the resultant spectrum shows the brilliant yellow lines of the metal sodium. Similar experiments made with the chlorides of strontium, calcium, lithium,' and other metals, give the bands due to the respective metals. When different salts are mixed together, and rammed into holes in the carbon, a spectrum is obtained which contains the bands of them all.

The position of these bright bands never varies, and each metal has its own system. Hence the competent observer can infer from the bands of the spectrum tin metals which produce it. It is a language addressed to the eye instead of the ear; and the certainty would not be augmented if each metal possessed the power of audibly calling out, "I am here!" Nor is this language affected by distance. If we find that the sun or the stars

The vividness of the colors of the lithium spectrum is extraordinary; the spectrum, moreover, contained a blue band of indescribable splendor. It was thought by many, during the discourse, that I had mistaken strontium for lithium, as this blue band had never before been seen. I have obtained it many times since; and my friend Dr. Miller, having kindly analyzed the substance made use of, pronounces it pure chloride of lithium.—J. T. give us the bands of our terrestrial metals, it is a declaration on the part of these orbs that such metals enter into their composition. Does the sun give us any such intimation? Does the solar spectrum exhibit bright lines which we might compare with those produced by our terrestrial metals, and prove either their identity or difference? No. The solar spectrum, when closely examined, gives us a multitude of fine dark lines instead of bright ones. They were first noticed by Dr. Wollaston, but were multiplied and investigated with profound skill by Fraunhofer, and named, after him, Fraunhofer's lines. They had been long a standing puzzle to philosophers. The bright lines yielded by metallic vapors had been also known to us for years; but the connection between both classes of phenomena was wholly unknown, until Kirchhoff, with admirable acuteness, revealed the secret, and placed it at the same time in our power to chemically analyze the sun.

We have now some difficult work before us. Hitherto we have been delighted by objects which addressed them-selves as much to our aesthetic taste as to our scientific faculty ; we have ridden pleasantly to the base of the final cone of Etna, and must now dismount and march through ashes and lava, if we would enjoy the prospect from the summit. Our problem is to connect the dark lines of Fraunhofer with the bright ones of the metals. The white beam of the lamp is refracted in passing through our two prisms, but its different components are refracted in different degrees, and thus its colors are drawn apart. Now, the color depends solely upon the rate of oscillation of the atoms of the luminous body, red light being produced by one rate, blue light by a much quicker rate, and the colors between red and blue by the intermediate rates. The solid incandescent coal-points give us a continuous spectrum; or, in other words, they emit rays of all possible periods between the two extremes of the spectrum. Color, as many of you know, is to light what pitch is to sound. When a violin-player presses his finger on a string he makes it shorter and tighter, and thus, causing it to vibrate more speedily, heightens the pitch. Imagine such a player to move his fingers slowly along the string, shortening it gradually as he draws his bow, the note would rise in pitch by a regular gradation; there would be no gap intervening between note and note. Here we have the analogue to the continuous spectrum, whose colors in-sensibly blend together without gap or interruption, from the red of the lowest pitch to the violet of the highest. But suppose the player, instead of gradually shortening his string, to press his finger on a certain point, and to sound the corresponding note; then to pass on to another point more or less distant, and sound its note; then to an-other, and so on, thus sounding particular notes separated from each other by gaps which correspond to the intervals of the string passed over; we should then have the exact analogue of a spectrum composed of separate bright bands with intervals of darkness between them. But this, though a perfectly true and intelligible analogy, is not sufficient for our purpose; we must look with the mind's eye at the oscillating atoms of the volatilized metal. Figure these atoms as connected together by springs of a certain tension, which, if the atoms are squeezed together, push them again asunder, and if the atoms are drawn apart, pull them again together, causing them, before coming to rest, to quiver for a certain time at a certain definite rate determined by the strength of the spring. Now, the volatilized metal which gives us one bright band is to be figured as having its atoms united by springs all of the same tension; its vibrations are all of one kind. The metal which gives us two bands may be figured as having some of its atoms united by springs of one tension, and others by springs of a different tension. Its vibrations are of two distinct kinds ; so also when we have three or more bands we are to figure as many distinct sets of springs, each capable of vibrating in its own particular time and at a different rate from the others. If we seize this idea definitely, we shall have no difficulty in dropping the metaphor of springs, and substituting, for it mentally the forces by which the atoms act upon each other. Having thus far cleared our way, let us make another effort to advance.

A heavy ivory ball is here suspended from a string. I blow against this ball; a single puff of my breath moves it a little way from its position of rest; it swings back toward me, and when it reaches the limit of its swing I puff again. It now swings further; and thus by timing the puffs I can so accumulate their action as to produce oscillations of large amplitude. The ivory ball here has absorbed the motion which my breath communicated to the air. I now bring the ball to rest. Suppose, instead of the breath, a wave of air to strike against it, and that this wave is followed by a series of others which succeed each other exactly in the same intervals as my puffs; it is obvious that these waves would communicate their motion to the ball and cause it to swing as the puffs did. And it is equally manifest that this would not be the case if the impulses of the waves were not properly timed; for then the motion imparted to the pendulum by one wave would be neutralized by another, and there could not be the accumulation of effect obtained when the periods of the waves correspond with the periods of the pendulum. So much for the particular impulses absorbed by the pendulum. But if such a pcndulum set oscillating in air could produce waves in the air, it is evident that the waves it would produce would be of the same period as those whose motions it would take up or absorb most completely, if they struck against it.

Perhaps the most curious effect of these timed impulses ever described was that observed by a watchmaker, named Ellicott, in the year 1741. He left two clocks leaning against the same rail; one of them, which we may call A, was set going; the other, B, not. Some time afterward he found, to his surprise, that B was ticking also. The pendulums being of the same length, the shocks imparted by the ticking of A to the rail against which both clocks rested were propagated to B, and were so timed as to set B going. Other curious effects were at the same time observed. When the pendulums differed from each other a certain amount, .A set B going, but the reaction of B stopped A. Then B set A going, and the reaction of A stopped B. When the periods of oscillation were close to each other, but still not quite alike, the clocks mutually controlled each other, and by a kind of compromise they ticked in perfect unison.

But what has all this to do with our present subject? The varied actions of the universe are all modes of motion; and the vibration of a ray claims strict brotherhood with the vibrations of our pendulum. Suppose ethereal waves striking upon atoms which oscillate in the same periods as the waves, the motion of the waves will be absorbed by the atoms; suppose we send our beam of white light through a sodium flame, the atoms of that flame will be chiefly affected by those undulations which are synchronous with their own periods of vibration. There will be on the part of those particular rays a transference of motion from the agitated ether to the atoms of the volatilized metal, which, as already defined, is absorption.

The experiment justifying this conclusion is now for the first time to be made before a public audience. I pass a beam through our two prisms, and the spectrum spreads its colors upon the screen. Between the lamp and the prism I interpose a snap-dragon light. Alcohol and water are here mixed with common salt, and the metal dish that holds them is heated by a spirit-lamp. The vapor from the mixture ignites and we have a monochromatic flame. Through this flame the beam from the lamp is now passing; and observe the result upon the spectrum. You see a shady band cut out of the yellow—not very dark, but sufficiently so to be seen by everybody present.

But let me exalt this effect. Placing in front of the electric lamp the intense flame of a large Bunsen's burner, a platinum capsule containing a bit of sodium less than a pea in magnitude is plunged into the flame. The sodium soon volatilizes and burns with brilliant incandescence. The beam crosses the flame, and at the same time the yellow band of the spectrum is clearly and sharply cut out, a band of intense darkness occupying its place. On withdrawing the sodium, the brilliant yellow of. the spectrum takes its proper place, while the reintroduction of the flame causes the band to reappear.

Let me be more precise. The yellow color of the spectrum extends over a sensible space; blending on one side with the orange and on the other with the green. The term "yellow band" is therefore somewhat indefinite. This vagueness may be entirely removed. By dipping the carbon-point used for the positive electrode into a solution of common salt, and replacing it in the lamp, the bright yellow band produced by the sodium vapor stands out from the spectrum. When the sodium flame is caused to act upon the beam it is that particular yellow band that is obliterated, an intensely black streak occupying its place.

An additional step of reasoning leads to the conclusion that if, instead of the flame of sodium alone, we were to introduce into the path of the beam a flame in which lithium, strontium, magnesium, calcium, etc., are in a state of volatilization, each metallic vapor would cut out a system of bands, corresponding exactly in position with the bright bands of the same metallic vapor. The light of our electric lamp shining through such a composite flame would give us a spectrum cut up by dark lines, exactly as the solar spectrum is cut up by the lines of Fraunhofer.

Thus by the combination of the strictest reasoning with the most conclusive experiment we reach the solution of one of the grandest of scientific problems—the constitution of the sun. The sun consists of a nucleus surrounded by a flaming atmosphere. The light of the nucleus would give us a continuous spectrum, like that of our common carbon-points; but having to pass through the photo-sphere, as our beam had to pass through the flame, those rays of the nucleus which the photosphere can itself emit are absorbed, and shaded spaces, corresponding to the particular rays absorbed, occur in the spectrum. Abolish the solar nucleus, and we should have a spectrum showing a bright line in the place of every dark line of Fraunhofer. These lines are therefore not absolutely dark, but dark by an amount corresponding to the difference between the light of the nucleus intercepted by the photo-sphere, and the light which issues from the latter.

The man to whom we owe this noble generalization is Kirchhoff, Professor of Natural Philosophy in the University of Heidelberg;' but, like every other great discovery, it is compounded of various elements. Mr. Talbot observed the bright lines in the spectra of colored flames. Sixteen years ago Dr. Miller gave drawings and descriptions of the spectra of various colored flames. Wheat-stone, with his accustomed ingenuity, analyzed the light of the electric spark, and showed that the metals between which the spark passed determined the bright bands in the spectrum of the spark. Masson published a prize es-say on these bands; Van der Willigen, and more recently Plucker, have given us beautiful drawings of the spectra, obtained from the discharge of Ruhmkorff's coil. But none of these distinguished men betrayed the least knowledge of the connection between the bright bands of the metals and the dark lines of the solar spectrum. The man who came nearest to the philosophy of the subject was Angstrom. In a paper translated from Poggendorff's "Annalen" by myself, and published in the "Philosophical Magazine" for 1855, he indicates that the rays which a body absorbs are precisely those which it can emit when rendered luminous. In another place, he speaks of one of his spectra giving the general impression of a reversal of the solar spectrum. Foucault, Stokes, and Thomson, have all been very close to the discovery; and, for my own part, the examination of the radiation and absorption of heat by gases and vapors, some of the results of which I placed before you at the commencement of this discourse, would have led me in 1859 to the law on which all Kirchhoff's speculations are founded, had not an accident withdrawn me from the investigation. But Kirchhoff's claims are unaffected by these circumstances. True, much that I have referred to formed the necessary basis of his discovery; so did the laws of Kepler furnish to Newton the basis of the theory of gravitation. But what Kirchhoff has done carries us far beyond all that had before been accomplished. He has introduced the order of law amid a vast assemblage of empirical observations, and has ennobled our previous knowledge by showing its relationship to some of the most sublime of natural phenomena.

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