But why have we to 'wait a little' before we see this effect? The thallium band at first almost masks the silver bands by its superior brightness. Indeed, the silver bands have wonderfully degenerated since the bit of thallium was put in, and for a reason worth knowing. It is the resistance offered to the passage of the electric current from carbon to carbon, that calls forth the power of the current to produce heat. If the resistance were materially lessened, the heat would be materially lessened; and if all resistance were abolished, there would be no heat at all. Now, thallium is a much more fusible and vaporizable metal than silver; and its vapour facilitates the passage of the electricity to such a degree, as to render the current almost incompetent to vaporize the more refractory silver. But the thallium is gradually consumed; its vapour diminishes, the resistance rises, until finally you see the two silver bands as brilliant as they were at first.[24]
We have in these bands a perfectly unalterable characteristic of the two metals. You never get other bands than these two green ones from the silver, never other than the single green band from the thallium, never other than the three green bands from the mixture of both metals. Every known metal has its own particular bands, and in no known case are the bands of two different metals alike in refrangibility. It follows, therefore, that these spectra may be made a sure test for the presence or absence of any particular metal. If we pass from the metals to their alloys, we find no confusion. Copper gives green bands; zinc gives blue and red bands; brass—an alloy of copper and zinc—gives the bands of both metals, perfectly unaltered in position or character.
But we are not confined to the metals themselves; the salts of these metals yield the bands of the metals. Chemical union is ruptured by a sufficiently high heat; the vapour of the metal is set free, and it yields its characteristic bands. The chlorides of the metals are particularly suitable for experiments of this character. Common salt, for example, is a compound of chlorine and sodium; in the electric lamp it yields the spectrum of the metal sodium. The chlorides of copper, lithium, and strontium yield, in like manner, the bands of these metals.
When, therefore, Bunsen and Kirchhoff, the illustrious founders of spectrum analysis, after having established by an exhaustive examination the spectra of all known substances, discovered a spectrum containing bands different from any known bands, they immediately inferred the existence of a new metal. They were operating at the time upon a residue, obtained by evaporating one of the mineral waters of Germany. In that water they knew the unknown metal was concealed, but vast quantities of it had to be evaporated before a residue could be obtained sufficiently large to enable ordinary chemistry to grapple with the metal. They, however, hunted it down, and it now stands among chemical substances as the metal Rubidium. They subsequently discovered a second metal, which they called Cæsium. Thus, having first placed spectrum analysis on a sure foundation, they demonstrated its capacity as an agent of discovery. Soon afterwards Mr. Crookes, pursuing the same method, discovered the bright green band of Thallium, and obtained the salts of the metal which yielded it. The metal itself was first isolated in ingots by M. Lamy, a French chemist.
All this relates to chemical discovery upon earth, where the materials are in our own hands. But it was soon shown how spectrum analysis might be applied to the investigation of the sun and stars; and this result was reached through the solution of a problem which had been long an enigma to natural philosophers. The scope and conquest of this problem we must now endeavour to comprehend. A spectrum is pure in which the colours do not overlap each other. We purify the spectrum by making our beam narrow, and by augmenting the number of our prisms. When a pure spectrum of the sun has been obtained in this way, it is found to be furrowed by innumerable dark lines. Four of them were first seen by Dr. Wollaston, but they were afterwards multiplied and measured by Fraunhofer with such masterly skill, that they are now universally known as Fraunhofer's lines. To give an explanation of these lines was, as I have said, a problem which long challenged the attention of philosophers, and to Professor Kirchhoff belongs the honour of having first conquered this problem.
(The positions of the principal lines, lettered according to Fraunhofer, are shown in the annexed sketch (fig. 55) of the solar spectrum. A is supposed to stand near the extreme red, and J near the extreme violet.)
Fig. 55.
The brief memoir of two pages, in which this immortal discovery is recorded, was communicated to the Berlin Academy on October 27, 1859. Fraunhofer had remarked in the spectrum of a candle flame two bright lines, which coincide accurately, as to position, with the double dark line D of the solar spectrum. These bright lines are produced with particular intensity by the yellow flame derived from a mixture of salt and alcohol. They are in fact the lines of sodium vapour. Kirchhoff produced a spectrum by permitting the sunlight to enter his telescope by a slit and prism, and in front of the slit he placed the yellow sodium flame. As long as the spectrum remained feeble, there always appeared two bright lines, derived from the flame, in the place of the two dark lines D of the spectrum. In this case, such absorption as the flame exerted upon the sunlight was more than atoned for by the radiation from the flame. When, however, the solar spectrum was rendered sufficiently intense, the bright bands vanished, and the two dark Fraunhofer lines appeared with much greater sharpness and distinctness than when the flame was not employed.
This result, be it noted, was not due to any real quenching of the bright lines of the flame, but to the augmentation of the intensity of the adjacent spectrum. The experiment proved to demonstration, that when the white light sent through the flame was sufficiently intense, the quantity which the flame absorbed was far in excess of that which it radiated.