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.
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.
Fig. 219.—Spectroscope with one Prism.