Popular Science Monthly/Volume 19/August 1881/The Teachings of Modern Spectroscopy

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THE TEACHINGS OF MODERN SPECTROSCOPY.[1]
By Dr. ARTHUR SCHUSTER, F. R. S.

A SCIENCE, like a child, grows quickest in the first few years of its existence; and it is therefore not astonishing that, though twenty years only have elapsed since Spectrum Analysis first entered the world, we are able to speak to-day of a modern spectroscopy, with higher and more ambitious aims, striving to obtain results which shall surpass in importance any of those achieved by the old spectroscopy, to the astonishment of the scientific world.

A few years ago the spectroscope was a chemical instrument. It was the sole object of the spectroscopist, to find out the nature of a body by the examination of the light which that body sends out when it is hot. The interest which the new discovery created in scientific and unscientific circles was due to the apparent victory over space which it implied. No matter whether a body is placed in our laboratory or a thousand miles away—at the distance of the sun or of the farthest star—as long as it is luminous and sufficiently hot, it gives us a safe and certain indication of the elements it is composed of.

To-day, we are no longer satisfied to know the chemical nature of sun and stars; we want to know their temperature, the pressure on their surface; we want to know whether they are moving away from us or toward us; and, still further, we want to find out, if possible, what changes in their physical and chemical properties the elements with which we are acquainted have undergone under the influence of the altered conditions which must exist in the celestial bodies. Every sun-spot, every solar prominence, is a study in which the unknown quantities include not only the physical conditions of the solar surface, but also the possibly changed properties, under these conditions, of our terrestrial elements. The spectroscope is rapidly becoming our thermometer and pressure-gauge ; it has become a physical instrument.

The application of the spectroscope to the investigation of the nature of celestial bodies has always had a great fascination to the scientific man as well as to the amateur ; for in stars and nebulæ one may hope to read the past and future of our own solar system. But it is not of this application that I wish to speak to-day.

As there is no other instrument which can touch the conditions of the most distant bodies of our universe, bodies so large that their size surpasses our imagination, so is there no other instrument which equals it in the information it can yield on the minute particles at the other end of the scale, particles which in their turn are so small that we can form no conception of their size or number. The range of the spectroscope includes both stars and atoms, and it is about these latter that I wish to speak.

The idea that all matter is built up of atoms, which we can not further divide by physical or chemical means, is an old one. As a scientific hypothesis, however—that is, an hypothesis which shall not only qualitatively, but also quantitatively, account for actual phenomena—it has only been worked out in the last thirty years. The development of molecular physics was contemporaneous with that of spectroscopy, but the two sciences grew up independently. Those who strove to advance the one paid little attention to the other, and did not trouble to know which of their conclusions were in harmony, which in discordance, with the results of the sister science. It is time, I think, now that the bearing of one branch of inquiry on the other should be pointed out : where they are in agreement, their conclusions will be strengthened, while new investigations will lead to more perfect truths where disagreement throws doubt on apparently well-established principles.

What I have ventured to call modern spectroscopy is the union of the old science with the modern ideas of the dynamical theory of gases, and includes the application of the spectroscope to the experimental investigation of molecular phenomena, which without it might for ever remain matters of speculation or of calculation.

A body, then, is made up of a number of atoms. These are hardly ever, perhaps never, found in isolation. Two or more of them are bound together, and do not part company as long as the physical state of the body remains the same. Such an association of atoms is called a molecule. When a body is in the state of a gas or vapor, each molecule for the greater part of the time is unaffected by the other molecules in its neighborhood, and therefore behaves as if these were not present. The gaseous state, then, is the one in which we can best study these molecules. They move about among each other, and within each molecule the atoms are in motion. Each atom, again, has its own internal movement. But, if the world were made up of atoms and molecules alone, we should never know of their existence; and, to explain the phenomena of the universe, we must recognize the presence of a continuous universal medium penetrating all space and all bodies. This medium, which we call the luminiferous ether, or simply the ether, serves to keep up the connection between atoms or molecules. All communications from one atom to another, and from one molecule to another, are made through this ether. The internal motions of one atom are communicated to this medium, propagated through space, until they reach another atom; attraction, repulsion, or some other manifestation takes place; and, if you examine any of the changes which you see constantly going on around you, and follow it backward through its various stages, you will always find the motion of atoms or molecules at the end of the chain.

The importance of studying the motion of molecules is therefore clear; and it is the special domain of the modern spectroscopy to investigate one kind of these motions.

When a tuning-fork or a bell is set in vibration, its motion is taken up by the surrounding air, waves are set up, they spread and produce the sensation of sound in our ears. Similarly, when an atom vibrates, its motion is taken up by the ether, waves are set up, they spread, arid if of sufficient intensity produce the sensation of light in our eyes. Both sound and light are wave-motions. A cursory glance at a wave in water will lead you to distinguish its two most prominent attributes. You notice at once that waves differ in height. So the waves both of light and sound may differ in height, and to a difference in height corresponds a difference in the intensity of the sound you hear or of the light you see. The higher the wave the greater its energy, the louder is the sound or the brighter is the light. But, in addition to a difference in height, you have noticed that in different waves the distance from crest to crest may vary. The distance from crest to crest is the length of the wave, and waves not only differ in height but also in length. A difference in the length of a wave of sound corresponds to a difference in the pitch of the sound; the longer a sound-wave is, the lower is the tune you hear. In the case of light a difference in the length of the wave corresponds to a difference in the color you see. The longest waves which affect our eyes produce the sensation of red, then follow orange, yellow, green, blue, and the shortest waves which we ordinarily see seem violet. If a molecule vibrates, it generally sends out a great number of waves which vary in length. These fall together on our retina, and produce a compound sensation which does not allow us to distinguish the elementary vibrations, which we want to examine. A spectroscope is an instrument which separates the waves of different lengths before they reach our retina; the elementary vibrations, after having passed through a spectroscope, no longer overlap, but produce their impressions side by side of each other, and their examination and investigation is therefore rendered possible.

The elements of spectroscopy will be familiar to most of you, but you will forgive me if I briefly allude to some points, which, though well known, are of special importance in the considerations which I wish to bring before you to-night.

When a body is sufficiently hot it becomes luminous, or, to speak in scientific language, the vibrations which are capable of producing a luminous sensation on our retina are increased in intensity as the temperature is raised, until they produce such a sensation. By means of a strong electric current I can in the electric lamp raise a piece of carbon to a high temperature. When looked at with the unaided eye it seems whitehot, but, when I send the rays through a prism and project them, as I do now, on a screen, you see a continuous band of light. This fact we express by saying that the spectrum of the carbon poles in the electric lamp is a continuous one. You see side by side the different colors known to you by the familiar but incorrect name of "the rainbow-colors"; and the experiment teaches you that the carbon pole of the electric lamp sends out rays in which all wave-lengths which produce a luminous sensation are represented.

But, if now I introduce into the electric arc a small piece of a volatile metal, you see no longer a continuous band of light. The band is broken up into different parts. Narrow bands or lines of different colors are separated by a space sometimes black, sometimes slightly luminous. The metal has been converted into vapor by the great heat of the electric current, and the vibrations of its molecules take place in distinct periods, so that the waves emanating from it have certain definite lengths. If the molecule could only send out one particular kind of waves, I should in its spectrum only see one single line. We know of no body which does so, though we know of several in which the possible periods of vibration are comparatively few; the spectrum of these will, therefore, contain a few lines only. Thus we have two different kinds of spectra, continuous spectra and line-spectra. But there is a certain kind intermediate in appearance between these two. The spectra of "fluted bands," as they are called, appear, when seen in spectroscopes of small dispersive powers, as made up of bands, which have a sharp boundary on one side and gradually fade away on the other. When seen with more powerful instruments, each band seems to be made up of a number of lines of nearly equal intensity, which gradually come nearer and nearer together as the sharp edge is approached. This sharp edge is generally only the place where the lines are ruled so closely that we can no longer distinguish the individual components. The edge is sometimes toward the red, sometimes toward the violet, end of the spectrum. Occasionally, however^ the fluted bands do not show any sharp edge whatever, but are simply made up of a series of lines which are, roughly speaking, equidistant. No one who has seen a spectrum of fluted bands can ever fail to distinguish it from the other types of spectra which I have described.

What, then, is the cause for the existence of these different types? The first editions of text-books in which our science was discussed stated that a solid or liquid body gave a continuous spectrum, while a gaseous body had a spectrum of lines; the spectra of bands were not mentioned. The more recent editions give a few exceptions to this rule, and the editions which have not appeared yet, will—so I hope, at least—tell you that the state of aggregation of a body does not directly affect the nature of the spectrum. The important point is not whether a body is solid, liquid, and gaseous, but how many atoms are bound together in a molecule, and how they are bound together. This is one of the teachings of modern spectroscopy. A molecule containing a few atoms only gives a spectrum of lines. Increase the number of atoms, and you will obtain a spectrum of fluted bands; increase it once more, and you will obtain a continuous spectrum. The scientific evidence for the statements I have made is unimpeachable. In the first place, I may examine spectra of bodies which I know to be compound. Special precautions often are necessary to accomplish this purpose, for too high a temperature would invariably break up the compound molecule into its more elementary constituents. For some bodies I may employ the low temperature of an ordinary Bunsen burner. With others, a weak electric spark taken from their liquid solutions will supply a sufficient quantity of luminous undecomposed matter to allow the light to be analyzed by a spectroscope of good power. The spectrum of a compound body is never a line-spectrum. It is either a spectrum of bands or a continuous spectrum. The spectra of the oxides, chlorides, bromides, or iodides of the alkaline earths, for instance, are spectra of fluted bands. All these bodies are known to contain atoms of different kinds—the metallic atoms of calcium, barium, or strontium, and the atoms of chlorine, bromine, iodine, or oxygen.

But to obtain these spectra of bands we need not necessarily have recourse to molecules containing different kinds of atoms. Elementary bodies show these spectra, and we must conclude therefore that the dissimilarity of the atoms in the molecule has nothing to do with the appearance of the fluted bands. Similarity in the spectrum must necessarily be due to a similarity in the forces which bind the atoms together, and this at once suggests that it is the compound nature of the molecule which is the true cause of the bands, but that the molecule need not be necessarily a compound of an atom with an atom of different kind, for it may be a compound of an element with itself. We have ample proof that this is the true explanation of the different types of spectra. I shall presently give you a few examples in support of the view which is now nearly unanimously adopted by spectroscopists.

I have hitherto left unmentioned one important method of investigating the periods of molecular vibrations, a method which is applicable to low temperatures. If I have a transparent body and allow light sent out by a body giving a continuous spectrum to fall through it, I often observe that the transparent body sifts out of the light falling through it certain kind of rays. Spectra are thus produced which are called absorption spectra, because the body which is under examination does not send out any light, but absorbs some vibrations which are made to pass through it. It is an important fact that a molecule absorbs just the rays which it is capable itself of sending out. I can therefore investigate the spectrum of a body just as well by means of the absorption it produces as by means of the light which it sends out.

Vapors like bromine or iodine examined in this way give us a spectrum of fluted bands. A powerful spark in these gases gives, however, a line-spectrum. Here, then, a change of spectrum has taken place. The same body at different temperatures gives us a different spectrum, and the change which takes place is the same as that observed in the spectrum of a compound body the moment the temperature has risen sufficiently to decompose that body. I conclude from spectroscopic observations, therefore, that the molecules of bromine and iodine just above their boiling-point are complex molecules, which are broken up at the temperature of the electric spark. At high temperatures the molecules of these bodies contain a smaller number of atoms, and it follows from this that the gases must be lighter or that their density must be smaller. These conclusions, which on spectroscopic grounds have been definite and clear for some years, have recently, by independent methods, been confirmed by Victor Meyer and others. It has been directly proved that at high temperatures the molecules of iodine and bromine contain a smaller number of atoms than they do just above their boiling-point. In other cases the change of density has not been directly proved, only because these necessary measurements are difficult or even impossible at very high temperatures, but we may be perfectly sure that chlorine, as well as the metallic vapors of silver, sodium, potassium, etc., which show an analogous change of their spectra, will ultimately be proved to undergo a change of density at high temperatures.

As we can trace the change from a line-spectrum to a band-spectrum taking place simultaneously with an increase of density, so may we follow the change from a band-spectrum to a continuous spectrum indicating the formation of a molecule still more complex.

Sulphur-vapor, at a temperature just above its boiling-point, contains three times the number of atoms in one molecule that it does at a temperature of 1,000º Centigrade. The spectrum of sulphur-vapor observed by absorption is continuous when the heavier molecule only is present. At the higher temperatures, when each molecule is decomposed into three, the spectrum belongs to the type of fluted bandspectra. From the cases in which we can thus prove the change in the spectra and in the densities to go on simultaneously, we are justified in concluding that also in other cases, where no such change of density has yet been observed, it yet takes place; and it is not a very daring generalization to believe that a change in spectra is always due to a change in molecular arrangement, and generally, perhaps always, accompanied by a change in the number of atoms which are bound together into one molecule.

With regard to the well-known statement that solids and liquids give continuous spectra, while gases give line-spectra, it must be remarked that metallic vapors show in nearly all cases a continuous spectrum before they condense. Oxygen gives a continuous spectrum at the lowest temperature at which it is luminous. Examining liquids and solids by the method of absorption, we find that many of them show discontinuous spectra, presenting fairly narrow bands. It is not denied that the nearness of molecules does not affect the spectrum. It may render the bands more wide and indistinct at their edges, but its influence is more of a nature which in gas spectra is sometimes observed at high pressures when the lines widen, and does not consist of an alteration in type. Though in a solid or liquid body the molecules are much nearer together, they are less mobile; and hence the number of actual collisions need not be necessarily much increased. The fact that a crystal may show a difference in the absorption spectrum according as the vibrations of the transmitted light take place along or across the axis, shows, I think, that mutual impacts can not much affect the vibrations, but that each molecule, at least in a crystal, must be kept pretty well in its place.

We have divided spectra into three types, but in all attempts at classification we are met by the same difficulty. The boundaries between the different types are not in all cases very well marked. Every one will be able to distinguish a well-defined band-spectrum from a line-spectrum, but there are spectra taking up intermediate positions both between the line-and band-spectra and between band-spectra and continuous spectra. With regard to these it may be difficult to tell to which type the spectrum really belongs. It may happen that a change of spectrum takes place, the spectrum retaining its type; but in these cases, as a rule, the more complex molecule will have a spectrum approaching the lower type, although it may not actually belong to that lower type. To be perfectly general, we may say that a combination of atoms always produces an alteration in the spectrum in the direction of the change from the line-spectrum, through the band spectrum to the discontinuous spectrum.

If we accept the now generally received opinion as to the cause of the different types of spectra, we may obtain information on molecular arrangement and complexity where our ordinary methods fail. At high temperatures^ or under much diminished pressure, measures of density become difficult or impossible; and it is just in these cases that the spectroscope furnishes us with the most valuable information. If we find three spectra of nitrogen and the same number for oxygen, we must accept the verdict, and conclude that these gases can exist in three different allotropic states.

Among the remarkable phenomena observed in vacuum-tubes, perhaps not the least curious is the spectrum observed at the negative pole, which in several cases is only observed there, and under ordinary circumstances in no other part of the tube. Both oxygen and nitrogen have a spectrum which is generally confined to the negative glow. Some years ago I tried to prove that also in these cases we have only to deal with a special modification of the gases which, curiously enough, only exists near the negative pole, and is broken up and decomposed in every other part of the tube. The experiments I then made seem to me to prove the point conclusively. After a current of electricity had passed through the tube for some time in one direction, the current was suddenly reversed; the negative pole now became positive, but the spectrum still was visible for some time in its neighborhood, and only gradually disappeared. This experiment shows that the spectrum may exist in other parts of the tube, and that it is therefore due to a peculiar kind of molecule, and not to anything specially related to electric phenomena taking place in the neighborhood of the negative pole. Other experiments supported this view.

The classification of spectra, according to the complexity of the vibrating molecule, is of great theoretical importance; for by its means we may hope to obtain some information on the nature of the forces which bind together the atoms into one molecule. Our whole life is a chemical process, and a great part of the mysteries of Nature would be cleared up if we could gain a deeper insight into the nature of chemical forces. I believe no other line of investigation to be as hopeful in this respect as the one which examines directly the vibrations of the molecules which take place under the influence of these chemical forces. If we could find a connection between the vibrations of a compound molecule and the vibrations of the simpler elements which it contains, we should have made a very decided step in the desired direction. I need not say that various attempts have been made to clear up so important a point; but we have to deal with complicated forces, and the attempts have as a rule not been crowned with much success.

There are, however, a few exceptions, a few cases of greater simplicity than the rest, where we are able to trace to their mechanical causes the spectroscopic changes which take place on chemical combination. These few and simple cases may serve as the finger-posts which show us the way to further research, and, we may hope, to further success. To make the spectroscopic changes of which I am speaking clear to you, I must have recourse to the analogy between sound and light, and remind you of the fact that when the prongs of a tuning-fork are weighted its tone is lowered, which means that the
Fig. 1.
PSM V19 D492 Spectral analysis of various materials.jpg

period of vibration is increased, and consequently that the length of the wave of sound sent out is lengthened. Now, suppose a molecule or atom, the spectrum of which I am acquainted with, enters into combination with another; and suppose that the vibrations of the second molecule are weak, or lie outside the visible range of the spectrum: then the most simple assumption which I could make would be that the addition of the new molecule is equivalent to an increase of the mass of the other. An increase of mass without alteration of the force of the molecule will, as in the case of the tuning-fork, lengthen the period of vibration, and increase the wave-length. If a case of that kind were actually to happen, I should observe the whole spectrum shifting toward the red; and this is what is observed in the few simple cases to which I have referred. The first observation to that effect is due to Professor Bunsen, of Heidelberg. Examining the absorption spectra of different didymium salts, he found such a close resemblance between them, that no difference could be detected with instruments of small powers; but with larger instruments it was found that the bands varied slightly in position, that in the chloride they were placed most toward the blue end of the spectrum, that when the sulphate was substituted for the chloride a slight shift toward the less refrangible end took place, and that a greater shift in the same direction occurred on examining the acetate. Prof. Bunsen remarks that the molecular weight of the acetate is larger than that of the sulphate, and that the molecule of the sulphate, again, is heavier than that of the chloride. He adds: "These differences in the absorption spectra of different didymium compounds can not, in our present complete state of ignorance of any general theory for the absorption of light in absorptive media, be connected with other phenomena. They remind one of the slight gradual alterations in pitch which the notes from a vibrating elastic rod undergo when the rod is weighted, or of the change of tone which an organ-pipe exhibits when the tube is lengthened." The accompanying woodcut (Fig. 1), copied from Professor Bunsen's paper, may serve to illustrate the shift observed in one of the absorption bands.

Similar changes take place when some substances like cyanin and chlorophyl are dissolved in different liquids. Absorption bands characteristic of these various substances appear, but they slightly vary in position. Professor Kundt, who has carefully examined this displacement of absorption bands, has come to the conclusion that as a rule the liquids of high dispersive powers were those which shifted the bands most toward the red end of the spectrum. But, though there is an apparent tendency in this direction, no rule can be given which shall be absolutely true whatever the substance which is dissolved. Fig. 2 shows the absorption spectrum of cyanin when dissolved in different

Fig. 2.
PSM V19 D493 Spectral analysis revealing chemical compounds.jpg
A = Absorption of Cyanin in Bisulphide of Carbon.
B =  " "  Nitrobenzene.
C =  " "  Benzene.
D =  " "  Ether.
E =  " "  Alcohol.

liquids. The measurements made by Claes[2] are employed. We have here an interesting proof that a solution is sometimes much more of a chemical compound than is generally supposed. The solvent and the substance must, indeed, be closely connected in order to produce a shifting of the absorption band. On the other hand, it is not astonishing that no general law can be given which connects the displacement with the physical properties of the solvent, for the closeness of connection depending on the special chemical affinity for each solvent has as much to do with the amount of shifting observed as the molecular weight or the dispersion or refractive power may have. The shifting of the absorption bands in different solutions of the same substances is only one of many applications of spectroscopes to the examination of molecular phenomena in liquids. Into the interesting researches of Professor Russell, who has greatly extended this field of inquiry, we have no time to enter.

The changes of spectra due to molecular combinations and rearrangements have in addition to their theoretical importance a great practical interest, for they will afford us some day a means of answering approximately a great many questions relating to the temperature of sun and stars. The gases and vapors in the solar atmosphere are for the greater part in the molecular condition in which they give a line-spectrum, and we know of stars the spectra of which resemble our solar spectrum very nearly. We shall not be far wrong in ascribing to such stars a temperature similar to that of our sun. Other stars have absorbing envelopes showing spectra of fluted bands. We know that fluted bands belong to a more complex molecular condition, which only can exist at lower temperatures. These stars, therefore, must have a lower temperature than our sun. Dr. Huggins, who has succeeded in obtaining most valuable photographs of star-spectra, has been able to classify and arrange star-spectra; and it is more than likely that, in the series of stars arranged in order by means of their spectra, we have at one end those of the highest, at the other those of the lowest, temperature. We are as yet far from being able to assign any particular temperature to a star, but the question by means of the spectroscope has been reduced to one which can be decided in our laboratories, and, however difficult it may be, we may rest assured that it will ultimately be solved. As to our sun, its temperature has been the subject of many investigations. Attempts have been made to deduce it (at least approximately) from the amount of heat it sends out. Different experimental laws have been proposed to connect together the heat radiation of a body, and the temperature of that body. The first law which was thus proposed gives 10,000,000º Centigrade as a lower limit; the second law reduces that lower limit to a little over 1,500º. Both these laws we now know to be wrong. More accurate laws give something like 10,000º or 20,000º, but the whole method employed is one which is open to a great many objections.

We measure the combined heat radiation of different layers on the solar surfaces, all of which are at different temperatures, and we ob; serve only an average effect which is much influenced by the absorption in the outer layers of the solar atmosphere and in the corona, and does not admit of easy interpretation. The spectroscopic method, which is yet in its infancy, has the advantage that we can observe separately each layer of the sun; and we thus examine the temperature not as an average, but for every part of the solar body. Our way to proceed would consist in carefully observing the spectra in different layers of the sun. Supposing we observe a change at one point, we may investigate at what temperature that change takes place, and we may then ascribe the same temperature to that particular place at the solar surface, if no other cause has interfered which may have affected our result. This last conditional limitation leads us to the discussion of the important but difficult question, whether we can determine any such interfering cause, which, not being temperature, yet produces the same change in a spectrum which we have hitherto only ascribed to changes of temperature.

I must here remark that a change in type is not the only spectroscopic change in the spectrum which is observed to take place on varying the temperature. Line-spectra especially are subject to curious variations in the relative intensities of their lines. These variations follow no general rule, and must be investigated separately for each element. The cause of this variation is a subject on which there exists a great difference of opinion; but, whatever this cause may be, if the changes always take place at one fixed temperature, we can turn them into account in measuring that temperature. However strong our wish that such a spectroscopic measurement of temperature may ultimately be obtained, a remarkable complication of facts has delayed the realization of this hope for at least a considerable period of time.

We have to enter partly into a theoretical question, and I must necessarily allude to some of the facts recognized by all who believe in the molecular theory of gases. Each molecule, which, as we have seen, sends out rays of light and heat on account of its internal motion, is surrounded by other molecules. These are, indeed, very closely packed, and continually moving about with enormous velocities. Generally they move in straight lines, but it must necessarily happen that often they come very near, and then affect and deflect each other. Perhaps they come into actual contact, perhaps they repel each other so strongly when near, that contact never takes place. The time elapsing between two such collisions is very small. If you can imagine one second of time to be magnified to the length of a hundred years, it would only take about a second, on the average, from the time a molecule has encountered one other molecule until it encounters the second. During the greatest part of this very short time, it moves in a straight line, for the forces between molecules are so small that they do not affect each other unless their distance is exceedingly small. It is, therefore, only during a very small fraction of time that one molecule is under the influence of another, and it is one of the greatest problems of molecular physics to find out what happens during that short element of time. I should like to explain to you how I believe the spectroscope may contribute its share to the settlement of that question. In his first great paper on the molecular theory of gases, the late Professor Clerk Maxwell assumed that two molecules may actually come into contact, that they may strike each other, as two billiard-balls do, and then separate, according to the laws of elastic bodies. This theory is difficult of application when a molecule contains more than one atom, and, especially as it did not in the case of conduction of heat give results ratified by the experimental test. Maxwell abandoned it in favor of the idea that molecules repel each other according to the inverse fifth power of the distance. This second theory not only gave what at the time was believed to be the correct law for the dependence of the coefficient of conduction on temperature, but it also helped its author over a considerable mathematical difficulty. Further experiments have shaken our faith in the first of these two reasons, and the second is not sufficient to induce us to adopt without further inquiry the new law of action between two molecules.

It is exceedingly likely that the forces acting between two molecules when they are in close proximity to each other are partly due to, or at least modified by, the vibrations of the molecules themselves.' Such vibrations must, as in the case of sound, produce attractive and repulsive forces, and vibrating molecules will affect each other in a similar way as two tuning-forks would. Now, if the forces due to vibrations play any important part in a molecular encounter, the spectroscope will, I fancy, give us some information. If two molecules of the same kind encounter, the periods of vibration are the same, and the forces due to vibration will remain the same during, perhaps, the whole encounter. If two dissimilar molecules encounter, the relative phase of the vibrations, and hence the forces, will constantly change. Attraction will rapidly follow repulsion, and the whole average effect will be much smaller than in the case of two atoms of the same kind. We have no clear notion how such differences may act, and we must have recourse to experiment to decide whether any change in the effect of an encounter is observed when a molecule of a different kind is substituted for a molecule having the same periods of vibration.

When a body loses energy by radiation, that energy is restored during an encounter; the way in which this energy is restored will profoundly affect the vibrations of the molecule, and hence the observed spectrum. I have endeavored by means of theoretical considerations, or speculations, as you may perhaps feel inclined to call them, to lead you on to an experimental law which I believe to be of very great importance. The spectrum of a molecule is in fact variable at any given temperature, and changes if the molecule is surrounded by others of different nature.

Placing a molecule in an atmosphere of different nature without change of temperature produces the same effect as would he observed on lowering of temperature.

Let me give you one example. Lithium at the temperature of the Bunsen flame has almost exclusively one red line in its spectrum. At the high temperature of the arc or spark the red line becomes weak, and almost entirely disappears. It is replaced by a strong orange line, which is already slightly visible, though weak, at low temperatures, and by additional green and blue lines.

But even at the high temperature of the spark we may obtain again a spectrum containing the red line only if we mix a small quantity of lithium with a large quantity of other material. The same spark, for instance, will give us the low-temperature spectrum of lithium when taken from a dilute solution of a lithium salt, and the high-temperature spectrum when that solution is concentrated.

The spectra of zinc and tin furnish us other examples in the same direction, but the spectra of nearly all bodies show the same law in a more or less striking way.

If this law which I have given you is a true one,[3] and I believe it will stand any test to which no doubt it will be subjected, we shall be able to draw some important conclusions from it. In the first place, it will be proved that the forces between atoms do depend on their vibrations. If this is true, any change in the vibrations of the spectrum, however small, will entail a corresponding change in all the other properties of the body. On the other hand, any change in the affinities of the element observed by other means will be represented by a change in the spectrum.

It is also possible that the introduction of forces due to vibratory motion will help us over a considerable difficulty in the molecular theory of gases. Some of the conclusions of that theory are at present absolutely contrary to fact. A spectroscopist, for instance, who is acquainted with the mercury spectrum and all the changes in that spectrum which can take place, feels more than skeptical when he is told that the molecule of mercury contains only one atom, which neither rotates nor vibrates.

Nor can it be of advantage to science to pass silently over this difficulty, or to neglect it as unessential, as is often done by modern writers. The late Professor Maxwell, at least, was well aware of its importance, and has often expressed in private conversation how serious a check he considered the molecular theory of gases to have received. This is not the place to enter more fully into this point, and to consider how the vibratory forces may affect some of the suppositions on which the theoretical consequences are founded.

However important the effects of concentration or dilution on the spectra may be, they render the spectroscope less trustworthy as a thermometric instrument; for, if the company in which a molecule is placed changes the spectrum in the same way as temperature would, it will be difficult to interpret our results. But, although the discussion of our observations may be rendered more arduous and complicated, we need not on that account despair. It is one of the problems of spectroscopy to find out the composition of bodies, not only qualitatively, but also quantitatively, and, when we shall know in what proportion different bodies are distributed in the sun, we may reduce the problem of finding out this temperature to the much simpler one of finding out the temperature of a given electric spark.

I hope that the few facts which I have been able to bring before you to-night have given you some idea of the important questions which have been brought under the range of spectroscopic research. Many of these questions still await an answer, some have only been brought into the preliminary stage of speculative discussion, but the questions have been raised, and the student of the history of science knows that this is an important step in its development and progress. The spectrum of a molecule is the language which that molecule speaks to us. This language we are endeavoring to understand. The inexperienced in a new tongue which he is trying to learn does not distinguish small differences of intonation or expression. The power over these is only gradually and slowly acquired. So it is in our science. We have passed by, and no doubt still are passing by, unnoticed differences which appear slight and unimportant, but which when properly understood will give us more information than the rough and crude distinctions which have struck us at first. We have extended our methods of research; we have extended our power over the physical agents; we can work with the temperature of sun and stars almost as we can with those in our laboratories. No one can foretell the result, and perhaps in twenty years time another lecturer will speak to you of a spectroscopy still more modern in which some questions will have received their definite answer, and by which new roads will have been opened to a further extension of science.

 
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  1. Address delivered at the Royal Institution of Great Britain, January 28, 1881.
  2. "Wied. Annalen," iii, p. 388, 1878.
  3. Lockyer, "Studies in Spectrum Analysis," p. 140, draws attention to the fact that an admixture of a second element dims the spectrum of the first, and he expresses this fact by saying, "In encounters of dissimilar molecules the vibrations of each are damped." Later he has shown that the lines of oxygen and nitrogen, which are wide at atmospheric pressure, thin out when the gases' are only present in small quantities. Lecoq de Boisbaudran in his "Atlas" gives several examples of the differences in the relative brilliancy of lines produced by concentrating or diluting the solution from which the spark is taken. The complete parallelism of this change to the changes produced by increased temperature has, however, never received sufficient attention.