Chapter XXIV: Introduction (22)

It was at one time objected to the theory which represents light as due to wave-like movements that, just as the vibrations which constitute sound spread in all directions, and go round intercepting bodies, enabling us, for example, to hear the sound of a bell even when a building intervenes, so if vibrations really produce light, these would extend within the shadows, and we ought to perceive light within the shadows, bending, as it were, round the edge of the shadow-casting body. This objection, which at one time presented a great difficulty for the wave theory, was triumphantly removed by the discovery that the luminous vibrations do extend into the shadow, and that this is in reality never completely dark. It is true that, although we can hear round a corner, we are in general unable to see round it; but it should be noticed that in the case of hearing, the sound is much weakened by intervening objects, and that there are what may be termed _sound shadows_. A ray of light produces sensible effects only in the direction of its propagation; but it can be shown that the successive portions of the waves advancing along it are centres of lateral disturbances producing new or secondary waves in all directions, which, however, interfere with and destroy each other. When an opaque screen intercepts a portion of the principal wave, it also stops a number of oblique or secondary waves, which would interfere more or less with the rest. Under ordinary circumstances, the remaining oblique or secondary rays are quite insensible in the presence of the direct light. But, with an apparatus which will cost but the two or three minutes’ time required to construct it, the reader may see for himself that light is able to _pass round an obstacle_, and he may witness directly phenomena of the same order as those presented in the experiment of Fresnel’s mirrors, which require costly apparatus for their production. He has only to take two fragments of common window-glass, and having made a piece of tinfoil adhere to one surface of each piece of glass, cut, with a sharp penknife, the finest possible slit in each piece of tinfoil, making the slit from ½ in. to 1 in. in length. If he will then hold one piece of glass about 2 ft. from his eye, so that it may be in the line between his eye and the sun (or other luminous body), and hold the other piece close to his eye with its slit parallel to that in the first piece, he will see the latter not simply as a line of light, but parallel to it a number of brilliantly-coloured rainbow-like bands will be seen on either side. If, instead of receiving the light from the sun, or from a candle-flame, the light given off by a spirit-lamp, with a piece of salt on its wick, be used, bright yellow stripes will be seen with dark spaces between them. Or, if the piece of glass next the sun be red-coloured, instead of plain glass, no rainbow-like bands will be visible, but a number of bright red stripes alternating with dark bands will be seen. The reader will have probably now little difficulty in perceiving that these can be easily explained as the results of interferences of a kind quite analogous to those of the waves of water represented in the diagram, Fig. 212. The rainbow-like stripes are due to the different wave-lengths of the different colours, as a consequence of which the bright and dark bands would be formed at different positions. Our limits do not admit of a full explanation of these beautiful effects, but the reader requiring further information would peruse with the greatest advantage portions of Sir John Herschel’s “Familiar Lectures on Scientific Subjects.”

The undulatory theory gives also an easy explanation of colours; they being, according to the theory, only the effects, as already stated, of the different rates of vibrations of the ether. If the ether particles perform 514,000,000,000,000 oscillations in a second, we receive the impression we call red colour; if they execute 750,000,000,000,000 vibrations, the impression produced on our organ of sight is different—we call it violet; and so on. Thus science teaches us that visual impressions so different as red, green, blue, violet, and other distinct colours, are, in reality, all due to movements of one and the same——something; and that the different sensations of colour we experience, arise merely from different rates of recurrence in these movements. In the subsequent article we shall have occasion to show that ordinary light, such as that of the sun, or of a candle, contains rays of every imaginable colour, mixed together in such proportions, that when this light falls upon a piece of paper, or upon snow, we have, in looking at these objects, the sensation of _whiteness_. But, if the light falls upon any substance which is able, in some way, to absorb or destroy some of the vibrations, the admixture of which makes up “_white light_,” as it is called, then that object sending back to our eyes the rays formed of the remaining group of vibrations, gives us the sensation of _colour_. Suppose, for example, a substance to be so constituted that it is capable of absorbing, or quenching in some way, all the vibrations of the ether which occur at a quicker rate than 520,000,000,000,000 in a second: such a substance would send back to our eyes only the vibrations which constitute red light (see table, page 411), and we should say the substance in question had a _red_ colour. Similarly, if the substance gave back only the vibrations which have the quickest rates, we should call the substance of a _violet_ character. The agent which produces in our visual organs the impression of colour is, therefore, not in the objects, but in the light which falls upon them. The rose is red, not because it has redness in itself, but because the light which falls upon it contains some rays in which there are movements that occur just the number of times per second that gives us the impression we call redness; in short, the colour comes not from the flower but from the light. “But,” the reader might say, “the rose is always red by whatever light I see it, and therefore the colour must be in the flower. Whether I view it by sunlight, or moonlight, or candlelight, or gaslight, I invariably see that _it is red_.” Now, it is precisely this circumstance—the seemingly invariable association of the object with a certain impression—in this case, redness—that leads our judgment astray, and makes us believe that the colour is in the object. Most people live out their lives without anything occurring to them which would give them the least idea that the colours of the objects they see around them are not in these objects themselves, but are derived from the light that falls upon the objects. And it required the comparison of many observations and experiments, and some clear reasoning, to establish a truth so unlike the most settled convictions of ordinary minds.

The point in question is fortunately one extremely easy of experiment, since we have simple means of producing light in which the vibrations corresponding to only one colour are present. The reader is strongly recommended to try the following experiment for himself. Let him procure a spirit-lamp, and place on the wick a piece of common salt about as large as a pea. Let the lamp be lighted in a room from which all other light is completely excluded, and bring near the flame a red rose or a scarlet geranium. The flower will be seen with _all its redness gone_—it will appear of an ashy grey or leaden colour. A ball of bright scarlet wool, such as ladies use to work brilliant patterns for cushions, &c., held near this flame, is apparently transformed into a ball of the homely grey worsted with which, about a century ago, old ladies might be seen industriously darning stockings. The experiment is, perhaps, even more striking when, a little distance from the spirit-lamp, is placed a feeble light of the ordinary kind, a rushlight for example. The ball of wool, held near the latter, shows vivid scarlet, but, brought near the spirit-lamp with the salted wick, is pale, ashy grey. Moving thus the ball of worsted, first to one light then to the other, gives a most convincing and striking proof of the entire illusion we are under as to colour being an inherent quality of substances. Similar experiments may be multiplied indefinitely. A bouquet, viewed by the rushlight, shows the so-called _natural_ colours of the flowers; viewed by the salted flame, roses, verbenas, violets, larkspurs, and leaves, all appear of the uniform ashy grey, and only _yellow_ flowers come out in their _natural_ colours. A picture, say a chromo-lithograph after one of the most gorgeous landscapes that Turner ever painted, appears a work in monochrome, and gives exactly the effect of a sepia or indian-ink drawing. The most blooming complexion vanishes, and the countenance assumes a cadaverous aspect very startling to persons of weak nerves; the lips especially, which might have rivalled pink coral by ordinary light, take a repulsive livid hue. All these effects may be seen to greater advantage by using the gas-flame of a Bunsen’s burner, having a lump of salt placed in the flame; or by means of a piece of _fine_ wire gauze, about six inches square, supported about two or three inches above an ordinary gas-burner, from which the gas is allowed to issue without being lighted, but when to the top of the wire gauze, which is strewed with small fragments of salt, a light is applied, the gas will ignite only above the gauze, without the flame passing down to the burner below.

A fuller explanation of these strange appearances may be gathered from the subsequent article; but it may suffice now to state that spirit, or gas burned in the way we have indicated, gives off little or no light of any kind. If, however, common salt be introduced into the flame, then light—but light of only one particular colour—is given off, and that colour is yellow. There are no red, or green, or blue, or violet vibrations given off; and as the objects on which the light falls cannot supply these, it follows that with this light no impression corresponding to these colours can be produced on the eye, whatever may be the objects upon which it falls. Such experiments, not simply read about but actually performed, cannot fail to convince an intelligent person that the colours come from the light and not from the object. Of course, it is not denied that there is in each substance something that determines which are the rays absorbed, and which are the rays reflected to the eye—something that can destroy certain waves, but is powerless over others that rebound from the substance, and reaching the eye, there produce their characteristic impressions. And it is but this power of sending back only certain rays among the multitude which a sunbeam furnishes, that can be attributed to objects when we say that they have such or such a colour. In this sense, then, we may properly say that _the rose is red_, but it is also at the same time undeniably true that _the redness is not in the rose_.

Let it not be supposed that such scientific conclusions as those we have arrived at tend in any way to rob Nature of her beauty, or that our sense of the loveliness of colour is in any danger of being blunted by thus tracing out, as far as may be, the causes and sources of our sensations. The poets have occasionally said harsh things of science—indeed, one goes so far as to stigmatize the man of science as one who would “untwist the rainbow” and “botanize upon his mother’s grave;” and another thus laments dispelled illusions:

“When Science from Creation’s face
Enchantment’s veil withdraws,
What lovely visions yield their place
To cold material laws!”

Now, in the case we have been considering, the scientific view is surely as beautiful as the ordinary one. We can, it is true, no longer regard the objects as having in themselves the colours which common observation attributes to them, but we look upon the material world as being, so to speak, the neutral canvas upon which Light, the great painter, spreads his varied tints, although, unlike the real canvas of an artist, which is not only neutral, but receives indifferently whatever hues are laid upon it, the objects around us exercise a selective effect—as if the picture of Nature were produced by each part of the canvas refusing all the tints save one, but itself supplying none. The tendency of the study of science to increase our interest in the great spectacle of Nature, and to enhance our appreciation of her charms, has been more justly indicated by another poet—thus:

“Nor ever yet
The melting rainbow’s vernal tinctured hues
To me have shone so pleasing, as when first
The hand of Science pointed out the path
In which the sunbeams gleaming from the west
Fall on the watery cloud, whose darksome veil
Involves the orient.”

FIG. 215.—_Portrait of Professor Kirchhoff._
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THE SPECTROSCOPE.

Many of the modern discoveries and inventions already described in these pages have been instances of practical applications of science to the every-day wants of mankind; but the chief interest of the subject we now enter upon flows mainly from other sources than direct applications of its principles in useful arts, although these applications are already neither few nor unimportant. But that which, in the highest degree, claims our attention and excites our admiration in the revelations of the spectroscope is the wonderful and wholly unexpected extent to which this instrument has enlarged our knowledge of the universe, and the apparently inadequate means by which this has been accomplished. A little triangular piece of glass gives us power to rob the stars of their secrets, and tells more about those distant orbs than the wildest imagination could have deemed attainable to human knowledge. One of the most acute philosophers of the present century, a profound thinker who devoted his mind to the consideration of the mutual relations of the sciences, declared emphatically, not very many years ago, that all we could know of the heavenly bodies must ever be confined to an acquaintance with their motions, and to such a limited acquaintance with their features as the telescope reveals in the less distant ones. A knowledge of their composition, he expressly asserted, could never be attained, for we could have no means of chemically examining the matter of which they are constituted. Such was the deliberate utterance of a man by no means disposed to underrate the power of the human mind in the pursuit of truth. And such might still have been the opinion of the learned and of the unlearned, but for the remarkable train of discoveries which has led us to the construction of instruments revealing to us the nature of the substances entering into the constitution of the heavenly bodies. We have now, for example, the same certainty about the existence of iron in our sun, that we have about its existence in the poker and tongs on the hearth. The last few years have seen the dawn of a new science; and two branches of knowledge which formerly seemed far as the poles asunder—namely, astronomy and chemistry—have their interests united in this new science of celestial chemistry. The progress which has been made in this department of spectroscopic research is so rapid, and the field is so promising, that the well-instructed juvenile of the future, instead of idly repeating the simple lay of _our_ childhood:

“Twinkle, twinkle, little star,
How I _wonder_ what you are!”

will probably only have to direct his sidereal spectroscope to the object of his admiration in order to obtain exact information as to what the star is, chemically and physically.

FIG. 216.
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The results which have already been obtained in celestial chemistry, and other branches of spectroscopic science, are so surprising, and apparently so remote from the range of ordinary experience, that the reader can only appreciate these wonderful discoveries by tracing the steps by which they have been reached. A few fundamental phenomena of light have already been spoken of in the foregoing article; and an acquaintance with these will have prepared the reader’s mind for a consideration of the new facts we are about to describe. In discussing, in the foregoing pages, the subject of refraction, we have, in order that the reader’s attention might not be distracted, omitted all mention of a circumstance attending it, when a beam of ordinary light falls upon a refracting surface, such as that represented in Fig. 203. The laws there explained apply, in fact, to elementary rays, and not to ordinary white light, which is a mixture of a vast multitude of elementary rays, red, yellow, green, &c. When such a beam falls obliquely upon a piece of glass, the ray is, at its entrance, broken up into its elements, for these, being refracted in different degrees by the glass, each pursues a different path in that medium, as represented by Fig. 216. Each elementary ray obeys the laws which have been explained, and therefore each emerges from the second surface of the plate parallel to the incident ray, and, in consequence of this, the separation is not perceptible under ordinary circumstances with plates of glass having parallel surfaces. But, if the second surface be inclined so as to form such an angle with the first that the rays are rendered still more divergent in their exit, then the separation of the light into its elementary coloured rays becomes quite obvious. Such is the arrangement of the surfaces in a prism, and in the triangular pieces of glass which are used in lustres.

For the fundamental experimental fact of our subject, we must go back two centuries, when we shall find Sir Isaac Newton making his celebrated analysis of light by means of the glass prism. We shall describe Newton’s experiment, for, although it was performed so long ago, and is generally well known, it will render our view of the present subject more complete; and it will also serve to impress on the reader an additional instance of the world’s indebtedness to that great mind, when we thus trace the grand results of modern discovery from their source. “It is well,” is the remark of a clear thinker and eloquent writer, “to turn aside from the fretful din of the present, and to dwell with gratitude and respect upon the services of ‘those mighty men of old, who have gone down to the grave with their weapons of war,’ but who, while they lived, won splendid victories over ignorance.”

FIG. 217.—_Newton’s Experiment._
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The experiment of Sir Isaac Newton will be readily understood from Fig. 217, where C is the prism, and A C represents the path of a beam of sunlight allowed to enter into a dark apartment through a small _round_ hole in a shutter, all other light being excluded from the apartment. In this position of the prism, the rays into which the sunbeam is broken at its entrance into the glass were bent upwards, and at their emergence from the glass they were again bent upwards, still more separated, so that when a white screen was placed in their path, instead of a white circular image of the sun appearing, as would have been the case had the light been merely refracted and not split up, Newton saw on the screen the variously-coloured band, D D, which he termed the _spectrum_. The letters in the figure indicate the relative positions of the various colours, red, orange, yellow, green, blue, &c., by their initial letters. The spectrum, or prolonged coloured image of the sun, is red at the end, R, where the rays are least refracted, and violet at the other extremity, where the refraction is greatest, while, in the intermediate spaces, yellow, green, and blue pass by insensible gradations into each other. Newton varied his experiment in many ways, as, for example, by trying the effect of refraction through a second prism on the differently coloured rays. He found that the second prism did not divide the yellow rays, for instance, into any other colour, but merely bent them out of the straight course, to form on the second screen a somewhat broader band of yellow, and similarly with regard to the others. From these, and a number of other experiments described in his “Opticks,” (A. D. 1675), Newton concludes, “that if the sun’s light consisted of but one sort of rays, there would be but one colour in the whole world, nor would it be possible to produce any new colour by reflections and refractions, and, by consequence, the variety of colours depends upon the composition of light.” ... “And if, at any time, I speak of light and rays, or coloured, or endued with colours, I would be understood to speak not philosophically and properly, but grossly, and accordingly to such conceptions as vulgar people in seeing all these experiments would be apt to frame. For the rays, to speak properly, are not coloured. In them there is nothing else than a certain power and disposition to stir up a sensation of this or that colour. For, as sound in a bell, a musical string, or other sounding body, is nothing but a trembling motion, and in the air nothing but that motion propagated from the object, and in the sensorium ‘tis a sense of that motion under the form of a sound; so colours in the object are nothing but a disposition to reflect this or that sort of rays more copiously than the rest: in the rays they are nothing but their dispositions to propagate this or that motion into the sensorium, and in the sensorium they are sensations of these motions under the form of colours.”

These memorable investigations of Newton’s have been the admiration of succeeding philosophers, and even poets have caught inspiration from this theme:

“Nor could the darting beam of speed immense
Escape his swift pursuit and measuring eye.
E’en Light itself, which everything displays.
Shone undiscovered, till his brighter mind
Untwisted all the shining robe of day;
And, from the whitening undistinguished blaze,
Collecting every ray into his kind,
To the charmed eye educed the gorgeous train
Of parent colours. First the flaming red
Sprung vivid forth; the tawny orange next;
And next delicious yellow—by whose side
Fell the kind beams of all-refreshing green;
Then the pure blue, that swells autumnal skies,
Ethereal played; and then, of sadder hue
Emerged the deepened indigo, as when
The heavy-skirted evening droops with frost,
While the last gleamings of refracted light
Died in the fainting violet away.
These, when the clouds distil the rosy show,
Shine out distinct adown the watery bow;
While o’er our heads the dewy vision bends
Delightful—melting on the fields beneath.
Myriads of mingling dyes from these result,
And myriads still remain.—Infinite source
Of beauty! ever blushing—ever new!
Did ever poet image aught so fair,
Dreaming in whispering groves, by the hoarse brook,
Or prophet, to whose rapture Heaven descends?”

The spectra which Newton obtained by admitting the solar beams through a circular aperture, were, however, not simple spectra. The circular beam may be considered as built up of flat and very thin bands of light, parallel to the edges of the prism, and a simple ray would be formed by one of these flat bands; as the round opening would allow an indefinite number of such rays to enter, each would produce its own spectrum on the screen, and the actual image would be formed of a number of spectra overlapping each other. When the aperture by which the light is admitted consists merely of a narrow slit, or line, parallel to the edges of the prism, we obtain what is termed a _pure spectrum_. When the prism is properly placed, an eye, viewing the fine slit through it, sees a spectrum formed, as it were, of a succession of virtual images of the slit in all the elementary coloured rays.

The person who first examined the solar spectrum in this manner was the English chemist Wollaston, who, in 1802, found that the spectrum thus observed was not continuous, but that it was crossed at intervals by dark lines. Wollaston saw them by placing his eye directly behind the prism. Twelve years later, namely, in 1814, the German optician Fraunhofer devised a much better mode of viewing the spectrum; for, instead of looking through the prism with the naked eye, he used a telescope, placing the prism and the telescope at a distance of 24 ft. from the slit, the virtual image of which was thus considerably magnified. The prism was so placed that the incident and refracted rays formed nearly equal angles with its faces, in which circumstance the ray is least deflected from its direction, and the position is therefore spoken of as being that of _minimum deviation_. It can be shown that this position is the only one in which the refracted rays can produce clear and sharp virtual images of the slit, and therefore it is necessary in all instruments to have the prism so adjusted. Fraunhofer then saw that the dark lines were very numerous, and he found that they always kept the same relative positions with regard to the coloured spaces they crossed; that these positions did not change when the material of which the prism was made was changed; and that a variation in the refracting angle of the prism did not affect them. He then made a very careful map, laying down upon it the position of 354 of the lines out of about 600 which he counted, and indicated their relative intensities, for some are finer and less dark than others. The most conspicuous lines he distinguished by letters of the alphabet, and these are still so indicated; and the dark lines in the solar spectrum are called “Fraunhofer’s Lines.” These lines, as will appear in the sequel, are of great importance in our subject. A few of the more obvious ones are shown in No. 1, Plate XVII. Fraunhofer found that these lines were always produced by sunlight, whether direct, or diffused, or reflected from the moon and planets; but that the light from the fixed stars formed spectra having different lines from those in the sun—although he recognized in some of the spectra a few of the same lines he found in the solar spectrum. The fact of these differences in the spectra of the sun and fixed stars proved that the cause of the dark lines, whatever it might be, must exist in the light of these self-luminous bodies, and not in our atmosphere. It was, however, some years afterwards ascertained that the passage of the sun’s light through the atmosphere does give rise to some dark bands in the spectrum; for it was found that certain lines make their appearance only when the sun is near the horizon, and its rays consequently pass through a much greater thickness of air.

Sir D. Brewster first noticed in 1832 that certain coloured gases have the power of absorbing some of the sun’s rays, so that the spectrum, when the rays are made to pass through such a gas before falling on the prism, is crossed by a series of dark lines—altogether different from Fraunhofer’s lines, though these are also present. The gas in which this property was first noticed is that called “nitric peroxide”—a brownish-red gas, of which even a thin stratum produces a well-marked series of dark lines. The same property was soon discovered in the vapours of bromine, iodine, and a certain compound of chlorine and oxygen. Each substance furnishes a system of lines peculiar to itself: thus the vapour of bromine, although it has almost exactly the same colour as nitric peroxide, gives a totally different set of lines. These, therefore, do not depend on the mere colour of the gas or vapour, and this is conclusively proved by the fact of many coloured vapours producing no dark lines whatever: the vapour of tungsten chloride, for example, although in colour so exactly like bromine vapour that the two cannot be distinguished by the eye, yields no lines whatever.

FIG. 218.—_Bunsen’s Burner on a stand._
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In Fig. 218 is represented a lamp for burning coal-gas, which is constantly used by chemists as a source of heat. It is known as “Bunsen’s burner,” from its inventor the celebrated German chemist. It consists of a metal tube, 3 in. or 4 in. long, and ⅓ in. in diameter, at the bottom of which the gas is admitted by a small jet communicating with the elastic tube which brings the gas to the apparatus. A little below the level of the jet there are two lateral openings which admit air to the tube. The gas, therefore, becomes mixed with air within the tube, and this inflammable mixture streams from the top of the tube and readily ignites on the approach of a flame, the mixture burning with a pale bluish flame of a very high temperature. This little apparatus is not only the most useful pieces of chemical apparatus ever devised, but it furnishes highly instructive illustrations of several points in chemical and physical science; and to some of these we invite the reader’s attention, as they have an immediate bearing on our present subject. Coal-gas is a mixture of various compounds of the two elementary bodies, hydrogen and carbon; and when the gas burns, these substances are respectively uniting with the oxygen of the air, producing water and carbonic acid gas. Now, when coal-gas is burnt in the ordinary manner as a source of light, the supply of oxygen is too small to admit of the complete combustion of all its constituents; and as the oxygen more eagerly seizes upon the hydrogen than upon the carbon, a large proportion of the latter thus set free from its hydrogen compound is deposited in the flame in the solid form, and is there intensely heated. The presence of solid carbon in an ordinary gas flame is easily proved by holding in it a cold fragment of porcelain, or a piece of metal, which will become covered with soot. In the flame of the Bunsen burner there is no soot, because the increased supply of oxygen, afforded by previously mixing the gas with air, enables the whole of the constituents of the gas to be completely burnt; and this is of the greatest advantage to the chemist, who always desires to have the vessels he heats free from soot, in order that he may observe what is taking place within them. The flame of Bunsen’s lamp becomes that of an ordinary sooty gas flame, when the two orifices which admit the air at the bottom of the tube are closed up, and then, of course, the temperature cannot be so high as when the whole constituents of the gas are completely burnt, but the flame becomes highly luminous; whereas when the orifices are open it gives so little light, that in a dark room one cannot see a finger held 20 in. from the lamp. Plainly the cause of this difference is connected with the presence or absence of the heated particles of solid carbon. The non-luminous flame contains no solid particles; the bright part of the other flame is full of them. To these heated particles of solid carbon we are, then, indebted for the light which burning coal-gas supplies. And, since we are able by such artificial illumination to distinguish colours, the white-hot carbon must give off rays of all degrees of refrangibility, and we should expect to find in the spectrum produced by such a flame, the red, yellow, green, and other coloured rays. And such is indeed the spectrum which these incandescent carbon particles produce: it resembles the solar spectrum, but _there is an entire absence of dark lines_, so that the appearance is that represented in No. 1, Plate XVII., if we suppose the Fraunhofer lines removed. If the pale blue flame of the Bunsen’s burner be similarly examined, the spectrum, No. 14, Plate XVII., shows that only a few rays of certain refrangibilities are emitted, forming bright lines here and there, but of little intensity, while the whole of the other rays are absent. This shows that while the highly heated solid gives off all rays from red to violet without interruption, the still more highly heated gases give off only a few selected rays.

It has long been known that some substances impart certain colours to flames, and such substances have been long employed to produce coloured effects in fireworks, &c. But coloured flames do not appear to have been examined by the prism until 1822, when Sir John Herschel described the spectra of strontium, copper, and of some other substances, remarking that “The colours thus communicated by the different bases to flame afford in many cases a ready and neat way of detecting extremely minute quantities of them.” A few years later, Fox Talbot described the method of obtaining a monochromatic flame, by using in a spirit-lamp diluted alcohol in which a little salt has been dissolved. The paper in which he describes this and other observations concludes thus: “If this opinion should be correct and applicable to the other definite rays, a glance at the prismatic spectrum of flame may show it to contain substances which it would otherwise require a laborious chemical analysis to detect.” Here we have the first hint of that spectrum analysis which has provided the chemist with a method of surpassing delicacy for the detection of metallic elements. The spectra of coloured flames were also subsequently examined and described by Professor W. A. Miller, but the most complete investigation into the subject was made by Professors Kirchhoff and Bunsen, who also contrived a convenient instrument, or _spectroscope_, for the examination and comparison of different spectra. The instrument has received many improvements and modifications, but the essential parts are one or more prisms; a slit, through which the light to be examined is allowed to enter; a tube, having at the other end a lens to render parallel the rays from the slit; a telescope, through which the spectrum is viewed; and usually some apparatus by which the positions of the different lines may be identified.

PLATE XVII. SPECTRA.
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FIG. 219.—_Spectroscope with one Prism._
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A very elegant instrument, made by Mr. John Browning, of the Strand, is represented in Fig. 219. It has a single prism, made of glass, of great power in dispersing the rays. The prism is supported on a little stage, placed in the middle of a horizontal circular brass table about 6 in. in diameter. On the left is seen a tube, about 15 in. long, at the outer extremity of which is the slit, formed of pieces of metal very accurately shaped. One of these pieces slides in a direction at right angles to the slit, and, by means of a spring and a fine screw, can be very nicely adjusted, so that an opening of any degree of fineness can be readily obtained. In front of the slit is a small glass prism, with its edges parallel to the slit, but only half its height. The bases of this prism are formed of two sides of a square and its diagonal, and, as shown in the figure, one side is parallel to the face of the slit, and the other to the axis of the tube. Rays of light coming from a source on the left of the slit (as seen in the figure) will, therefore, enter this little prism, and be totally reflected (see page 399) by the diagonal surface, down the axis of the tube through the lower half only of the slit. This is the only office of this prism, which has nothing to do with the dispersion of the rays: the use to which it is put will be seen presently. It is fixed in such a manner that, when required, it can be turned aside with the touch of a finger, and the _whole_ length of the slit exposed. A peculiarity in these instruments of Mr. Browning’s is the admirable arrangement for determining the position of any line in a spectrum. For this purpose, the eye-piece of the telescope is provided with a pair of cross-wires, and the telescope itself, which is about 18 in. in length, moves in a horizontal plane round the axis of the circular brass table, from which an arm projects, carrying a ring into which the telescope screws. This arm carries a _vernier_ along the limb of the circular table, which is very accurately divided into thirds of degrees, so that with the aid of the vernier the angular position of the telescope can be read off to a minute, that is, to 1/60th of a degree. The arm carrying the telescope is provided with a screw for clamping it in any desired position while the readings are taken. On placing in front of the slit the flame of a Bunsen’s burner, the spectrum produced by any substance in this flame will, when the instrument is in proper adjustment, be seen on looking through the telescope, and the cross-wires being also in view, the point of their intersection may be brought into coincidence with any line of the spectrum, and the telescope being clamped in this position, the angular reading thus taken determines the position of the line. Thus, for example, the angular positions in which the principal Fraunhofer’s lines are seen having been observed and recorded, the angular position of any line in another spectrum will at once determine its position among the Fraunhofer lines; or the spectrum may be mapped by laying down the angular readings of the lines by means of a scale of equal parts. And, again, in the little prism in front of the slit we have the means of bringing two spectra in view at once, one being from a light directly in front, and the other from a light at the side. The two spectra are seen one above the other, and the coincidence or difference of their lines may be directly observed. When the instrument is in use, the prism and the ends of the tube are covered with a black cloth, loosely thrown over them, by which all stray light is shut out. The author has had in use for several years one of these instruments, and he cannot forbear expressing his perfect satisfaction with its powers, which he finds amply sufficient for all ordinary chemical purposes, while the accuracy of the workmanship is really wonderful, considering the very moderate price of the instrument.

The substances the spectra of which are most conveniently examined are the metals of the alkalies and alkaline earths. Small quantities of the salts of these metals, placed in a loop of fine platinum wire, impart characteristic colours to the flame of a Bunsen burner or to that of a spirit-lamp. For the examination of the spectra the former is to be preferred, as the lines come out much more vividly. Indeed, at temperatures higher than that of the Bunsen’s burner, such as in the flame of pure hydrogen, or in the voltaic arc, some substances give out additional lines. In Plate XVII., Nos. 2 to 9, is shown the appearance of the spectra produced by the Bunsen’s burner when salts of the metals are held in the flame in the manner already mentioned, and the spectra are examined with the instrument just described. One of the simplest of these spectra is that produced by sodium compounds, such as common salt. The smallest particle of this substance imparts an intense yellow colour to the flame, and the spectrum is found to take the form of a single bright yellow line—No. 3. It has been estimated that the presence of the (1/100000000)_th part of a grain_ of sodium can be detected by the production of this line. Indeed, the very delicacy of this sodium reaction renders it almost impossible to get rid of this line, for sodium is found to be present in almost everything,—a fact the earlier observers of spectra were not aware of, for they attributed this yellow line to water, which was the only substance they knew to be so generally diffused. If a platinum wire be heated in the flame of the Bunsen burner until all the sodium indications have disappeared, it suffices to remove the wire, and, without allowing it to come into contact with anything, to leave it exposed to the air for a few minutes, to cause it again to give the characteristic yellow colour when again plunged into the flame. This is due to the fact that the element is contained in all the floating particles which pervade the atmosphere. The spectroscope is not required to show the presence of the sodium on the platinum which has been exposed to the air, the colour imparted to the flame being plainly visible to the eye, and it needs only the Bunsen burner and 2 in. of platinum wire to prove the fact, and also to show that mere contact with the fingers is enough to highly charge the wire with sodium compounds. Any volatile compound of potassium gives the spectrum represented by No. 2, the principal lines being a red line and one in the extreme violet, the latter being somewhat difficult to observe. There is also a third rather ill-defined red line, and a portion of a faint continuous spectrum. Salts of strontium impart a bright red colour to the flame, and the spectrum they produce is shown by No. 6, in which are seen several bright red lines and a fainter blue one. Calcium, which also gives a reddish colour to flame, furnishes an entirely different set of lines (No. 5), and barium salt another, containing numerous lines, especially some very vivid green ones.

In all the cases we have named, and whenever bright-lined spectra are furnished by substances placed in the flame of a lamp, or in burning hydrogen gas, or in the intensely hot voltaic arc, there is evidence that the substances are converted into vapour or gas. We have already seen how hot solid carbon gives a continuous spectrum, while carbon in the state of gaseous combination gives most of the bright lines seen in the spectrum of coal-gas (No. 14). It is observed also that the more readily volatized are the salts, the more vivid are the bright lines they produce when heated in a flame. It must be understood that each element gives it own characteristic lines, that these are always in precisely the same position in the spectrum, that no substance produces a line in exactly the same position as another, however near two lines due to different substances may, in some cases, appear; and also, that however the salts of the different metals are mixed together, each produces its own lines, and each ingredient may be recognized. And this is done in an instant by an experienced observer—a mere glance at the superposed spectra of, perhaps, half a dozen metals, suffices to inform him which are present. There is also a peculiarity in this optical mode of recognizing the presence of bodies which gives the subject the highest interest, namely, the circumstance that the spectrum is produced and the bodies recognized, however far from the observer the luminous gas may be placed, the only condition required being that the rays reach the instrument.

Until Kirchhoff and Bunsen’s spectroscopic investigations, lithium was supposed to be a rare metal, occurring only in a few minerals. It happens that this substance yields a remarkable spectrum (No. 4), for it gives an extremely vivid line of a splendid red colour, accompanied by only one other, a feeble yellow line; and the reaction is of very great delicacy, for 1/6000000 of a grain can easily be detected, and an eye which has once seen the red line readily recognizes it again. A single drop of a mineral water containing lithium has been found to distinctly produce the red line, in cases where the quantity contained in a quart of the water would have escaped ordinary chemical analysis. The spectroscope has shown that lithium, so far from occurring in only four or five minerals, is a substance very widely diffused in nature. In the waters of the ocean, in mineral and river waters, in most plants, in wines, tea, coffee, milk, blood, and muscle, this metal has been found. Dr. Roscoe states that the ash of a cigar, when moistened with hydrochloric acid, and held in a platinum wire in the flame of the Bunsen’s burner, at once shows the principal lines of sodium, potassium, calcium, and lithium. Salts of lithium and of strontium both impart a rich crimson tint to flames, and it is hardly possible to detect any difference in these colours with the naked eye; but, as the reader may see on comparing spectra No. 4 and No. 6, the prism makes a wide distinction.

Matter for a very interesting chapter in the history of prismatic analysis has been furnished by the discovery of four new elements by means of the spectroscope. In 1860 Bunsen observed that the residue, after evaporation, of a certain mineral water, yielded spectra with bright lines which he had not seen before. He concluded that they were due to some unknown elements, and, in order to separate these, he evaporated many tons of the water, and was rewarded by the discovery of two alkaline metals, _cæsium_ and _rubidium_. The delicacy of the spectrum reaction may be inferred from the fact of a ton weight of the water containing only three grains of the salts of each of these substances. Rubidium gives a splendid spectrum, containing red, yellow, and green lines, and also two characteristic violet lines; while cæsium has orange, yellow, and green lines, and two very beautiful blue lines, by which it is easily recognized.

About the same time, Mr. W. Crookes discovered, in a mineral from the Hartz, another elementary body, the existence of which was first indicated to him by the characteristic spectrum it produces, namely, a single splendid green line (No. 8 spectrum). In 1864 two German chemists discovered, also in the Hartz, a fourth new element, which was detected by two well-defined lines in the more refrangible end of the spectrum—(see spectrum No. 9, in the plate). This metal was named Indium, in reference to the colour of its lines, and the names of the other three—cæsium, rubidium, and thallium, are also derived from the colours of their characteristic lines.

FIG. 220.—_Miniature Spectroscope._
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Although the reader may, from such representations of the spectra as those given in Plate XVII., form some idea of their appearance, he would find his knowledge of the subject much clearer if he had the opportunity of examining for himself the actual phenomena. We have already recommended the performance of certain easy experiments involving no outlay, but, in the matter of spectroscopes, carefully finished optical and mechanical work is absolutely necessary in the appliances. It fortunately happens that one eminent optician, at least, has made it his study to produce good spectroscopic apparatus at the lowest possible cost, and if the reader be interested in this subject, and desirous of trying experiments himself, he can, for a very moderate sum, be equipped with all the appliances for examining the phenomena we have described. He has only to procure, in the first place, a small direct-vision spectroscope, such as that represented of its actual size in Fig. 220, which is sold by Mr. Browning for twenty-two shillings; secondly, a Bunsen’s burner, a few feet of india-rubber tubing, two inches of platinum wire, and a few grains of the salts of lithium, strontium, thallium, &c. The whole expense will probably be covered by adding four shillings to the cost of the spectroscope, and the reader will then be in a position to see for himself the principal Fraunhofer lines, the spectra of the metals already referred to, and the absorption bands of the gases which have been mentioned, as well as the absorption bands in liquids which will be spoken of in the sequel.

FIG. 221.—_The Gassiot Spectroscope._
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The splitting up of a beam of light into its elements—which it is the office of the prism to produce—is accomplished by a single prism to a certain degree only. It separates the red from the green, for example; but the colours pass into each by insensible gradations through orange, yellow, and greenish yellow. If we allow the rays to fall upon a second prism after emerging from the first, the separation is carried further; the red, for instance, is spread out into different kinds of red, and so on with the rest. And the greater the number of prisms, the greater is the extension which is given to the spectrum. Now, just as by increasing the power of the telescope, new stars become visible, whose light was before too faint, and nebulæ, or stars which before seemed single, are resolved into clusters of individual stars—so, by increasing the power of the spectroscope by employing two, four, or more prisms, lines which appear single by the less powerful instruments are, in some instances, resolved into groups of lines, and new lines come into view, which before were too faint to show themselves. For example, if we view the Fraunhofer lines through a spectroscope like that in Fig. 220, but having two prisms instead of one, we shall see that the D line is not really a single line, but is formed of two lines close together. If we use greater dispersive power by employing a greater number of prisms, we shall observe with solar light that when these two D lines are sufficiently separated, several other lines make their appearance between them. In this way the number of dark lines in sunlight, which have been carefully mapped by Kirchhoff and others, amount to upwards of 2,000; and no doubt there are many more lines waiting a still more powerful instrument. Fig. 221 is copied from a large spectroscope made by Mr. Browning for Mr. Gassiot. It has nine or more highly dispersive glass prisms; the telescope and the tube bearing the slit have focal lengths of 18 in., the lenses having a diameter of 1½ in.; the telescope is provided with a slow motion for taking the angular position; and there is a third tube provided with a micrometer, by which the position of the lines can be measured to 1/10000th of an inch.

The instruments we have mentioned, except the miniature spectroscope, show only a portion of the spectra at once, a movement of the telescope being requisite to bring each part into view. It has been already stated that the only position of the prism which will make the lines clear and well defined is that in which the _deviation_ is the least. In using trains of prisms it is therefore necessary to adjust each prism for the part of the spectrum which may be under observation. This is a tedious process, and it has been obviated by a useful invention of Mr. Browning’s, by which the adjustment is rendered automatic—that is, the movements of the telescope are communicated to the prisms in such a manner that they place themselves into the proper position for producing clear images of the slit, whatever may be the refrangibility of the rays under examination: Fig. 222 shows the arrangement as it appears when viewed from above. The train of six prisms can be so arranged that the ray after passing through six of them shall be totally reflected by a surface of the last prism, and pursue again its path through the six prisms in the reverse direction, becoming more and more dispersed by each prism until it emerges parallel to the axis of the telescope. The power of the instrument is, therefore, equivalent to that of one with twelve prisms; but it can be used at pleasure with any dispersive power, from two to twelve prisms.

FIG. 222.—_Browning’s Automatic Adjustment of Prisms._
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