Discoveries and Inventions of the Nineteenth Century

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 426spectroscope. 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. 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 427gases 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. 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, 428and 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 110000th 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. By making use of one of the Bunsen burners, the lines which are characteristic of some ten or twelve metals are readily seen when one of their more volatile salts is converted into vapour. For this purpose their chlorides are usually employed, but the reactions are common to all their salts. It is necessary that the metal should exist in the flame in the state of highly heated vapour or gas, in order that its characteristic rays should be given 429off. We usually introduce compounds of these metals into the flame; but there is reason to believe that these are decomposed in the flame, and the disassociated metal takes the form of glowing gas, a small quantity of which suffices for the production of the bright lines. No doubt the other constituent of the compound, the chlorine for example, is also set free in the gaseous form; but since the spectrum of the metal only is visible, we may infer that at the temperature of the flame, the non-metallic elements are not sufficiently luminous to produce a spectrum. When we repeat the experiments with salts of the less volatile metals, we obtain no spectra—the temperature of the flame not being sufficiently high to convert these into vapour. Other methods have, therefore, to be resorted to, and advantage is taken of the fact discovered by Faraday, that an electric spark is nothing but highly heated matter. The spectroscope gives us reason to believe that this matter, which is formed of the substances between which the spark passes, is in the gaseous state; for it is found, on examining sparks passing between two pieces of each metal, that characteristic bright lines are produced. If one of the metals already named is submitted to this examination, the same lines are found which are seen in the spectra produced by the salts of the metal volatized in the flame, but in some cases additional bright lines appear in the spark spectrum. With the heavier metals the spark, or the electric arc, is, however, the only means of igniting their vapours. The usual mode of doing this is to make the discharges of a large induction coil pass between the two fine wires of the metals, placed about a quarter of an inch apart. A Leyden jar is commonly employed to condense the discharge, and thus produce a still higher temperature. Mr. Browning has contrived the neat little apparatus shown in Fig. 223, in which the jar is superseded by a more compact and convenient condenser 430inside of the box, so that it is only necessary to attach one terminal of the coil to the binding-screw, seen outside of the end of the box, and place the other wire from the coil in the binding-screw of one or the other of the pieces of apparatus supported by the upright rod. Of these it is the one on the right which at present engages our attention. Within a small glass cylinder are two sliding rods, terminated by screw-clips, which hold finely-pointed pieces of the metal under examination. The slit of the spectroscope is placed close to the glass cylinder, and when a very rapid succession of sparks is passing, the bright lines are seen continuously. The spectra of metals examined in this way are found to yield a very large number of lines. Thus the spectrum of calcium has 75 lines, and that of iron no fewer than 450 lines. Our limits will not permit of an account of many interesting particulars relating to these spectra, which include those of all the 50 metallic elements. It should, perhaps, be stated that a modified mode of producing spectra by sparks is sometimes found useful. This consists in causing sparks to pass between a solution of some salt of the metal and a