Mr. Wheatstone had perceived that the bright lines on the spectra of the metals are different and more complicated when taken in air than in vacuo, and Professor Angström made the important remark that the electric spark gives two superposed spectra, one due to any metal that may be under examination, the other to the incandescence of the air through which the spark passes. Hence the importance of the spectrum analysis of gaseous substances, especially of those which constitute our atmosphere, a subject that has been ably and successfully investigated by Professor Plücker. For that purpose he made use of the Geissler or vacuum tubes, similar to those he used in his experiments on the stratification of electric light. When electricity was sent through a tube containing oxygen gas, the gas combined so rapidly with the platinum of the negative terminal of the battery that there was little time to examine the spectrum. The electral light in the tube was too red at first, but as the attenuated gas gradually disappeared it changed through flesh-colour to green, then through blue to reddish-violet, and at length there was too little gas to convey the electricity. However, the oxygen spectrum has a remarkably bright red band at its red extremity, two bright orange lines divided by a black one in the orange, and some bright bands in the green.
The electric light of attenuated hydrogen is red, and almost the whole light in its spectrum is concentrated into six bright bands of nearly equal breadths. There is a dazzling red band near the red end of the spectrum, which, however, does not coincide with the oxygen band; then comes a very beautiful yellow band, in which the whole of the yellow rays seem to be concentrated, followed by a grey interval which separates the yellow from three bright lines in the green, the first of which is yellowish green, the last a beautiful greenish blue; a black and a dark space separates the latter from the violet in which there is a bright line. The electric light in a tube containing highly rarefied aqueous vapour is red, the vapour is resolved into its simple elements by the electricity, the oxygen combines with the platinum of the negative or heat pole, and the spectrum is that of pure hydrogen with the three most prominent bands only.
The nitrogen spectrum is brilliant with all the seven colours; there are no broad dark spaces like those which divide the bright bands in the hydrogen spectrum, but it is crossed by numerous very fine black and grey lines. Fifteen of the latter stripe the red and orange; the green is separated from the yellow by a black narrow band; it is terminated by two bright blue lines, and very fine dark lines cross it and the rest of the spectrum. The tube light is yellowish red.
The spectrum of highly rarefied atmospheric air is chiefly that of nitrogen, for the oxygen combines with the platinum of the negative terminal, and is in too small a quantity to transmit the electricity through the tube.
The rarefied vapours of chlorine, bromine, and iodine are so rapidly combined with the platinum of the negative terminal, that it is difficult to determine their spectra; but they have peculiarities in common, which distinguish them from all other spectra. The bright lines that cross them are first at rest, but soon become flickering. In the iodine spectrum, five of those lines of flickering light of great beauty are in the green, two of them close together. The bromine spectrum shows a greater number, which extend across the colours of its middle part, accompanied by dark lines; and in the chlorine spectrum there are many lines, both of flickering light and darkness. New lines are brought out in the iodine spectrum by increase of temperature. At a low heat it is crossed by a number of dark lines, but with a higher temperature the vapour has a greenish hue, which is resolved by the prism into green lines at some distance from one another, and fainter blue light, crossed by groups of luminous bands.
Rarefied compound gases are resolved by the electricity into their component parts, and the result is superposed spectra, one belonging to each element. M. Seguin considers the aspect of the electric spark to be a sure indication of chemical action, for while the decomposition is in progress, the electric spark is encompassed by a halo, and the bright lines of the double spectrum are less distinct; but when the reaction is finished, the spark becomes slender, and the spectrum bands distinct. In the decomposition of highly carburetted and attenuated hydrogen gas, the spark resembles a flame, and the spectrum is like that of white light. When the gas is decomposed, the hydrogen is disengaged, and the carbon deposited on the extremities of the conducting wires; the spark becomes slender, and then the lines of the hydrogen, the lines belonging to the hydro-carbon and to carbon itself may be seen on the spectrum.[[17]]
The bright and coloured lines on the spectra of the gases, and the vapours of a great number of the metals and metallic salts, were known before MM. Bunsen and Kirchhoff began their systematic researches, during which they added many more, some so difficult and analogous, that it required all their skill and experience to make them out.
Of all the spectra that have been determined, those of sodium and iron are the most important and interesting. In that of sodium, the only light is of the purest yellow condensed into a double line of intense brilliancy on a dark ground. The iron spectrum on the contrary is crossed by bright lines of all intensities and colours in such multitudes, that their number has not been ascertained. The calcium spectrum has one very bright green band in the orange, a red line in the yellow, and a well-defined yellow line in the indigo. As already mentioned, the red and orange parts of the strontium are crossed by many red lines separated by dark intervals; there is a bright blue line between the orange and yellow, and an orange line in the blue. One intense crimson band in the orange characterises the lithium spectrum. Seven broad green bands stripe the yellow and a part of the green, in the barium spectrum, and that of magnesium has many green bands and lines.
All of these were determined by the heat of white coal gas flame, which amounts to 2350° Cent., and at the time MM. Bunsen and Kirchhoff were not aware that by an increase of temperature new bright lines were added to some of the spectra. That discovery was made by Professor Tyndall, while examining the spectrum of chloride of lithium, which with the low temperature has only one crimson band in the orange, but with the hotter flame of hydrogen gas, amounting to 3259° Cent., an orange line appeared in the yellow, and when Mr. Tyndall employed the electric lamp,[[18]] the spectrum acquired a broad brilliant blue band between the orange and yellow, while the crimson band remained unchanged. Professors Roscoe and Clifton confirmed Tyndall’s discovery, and upon comparing the spectra of strontium and lithium, they found where only one prism was employed that the blue line of lithium appeared to coincide with the blue line, delta, of strontium; but with an apparatus having several prisms like that of Kirchhoff, they saw that the two blue lines differed by one division of the measuring scale, the lithium line being the most refrangible. A great change was produced on the strontium spectrum by increased electric temperature: three of the red bands vanished, and new bright lines appeared, that were not coincident with those they replaced; the blue line was not affected, but four new violet lines were added. With the intense heat of the electric spark, the broad green band of the calcium spectrum is replaced by five green lines of less refrangibility, the well-defined yellow line vanishes, and instead of the red band three red or orange lines appear, of greater refrangibility than those that have vanished. Six of the bright green bands in the spectrum of barium entirely vanish, and bright new non-coincident lines appear. Thus, not only new lines appear at very high temperature, but the broad bands, characteristic of the metal or metallic compound at a low temperature of the flame or a weak spark, totally disappear at the higher temperature. The new bright lines, which supply the part of the broad bands, are generally not coincident with any part of the band, sometimes being less and sometimes being more refrangible. The gentlemen who made these experiments add, that possibly the cause of the disappearance of the broad bands and the production of the bright lines may be, that at the lower temperature of the flame or weak spark, the spectrum observed is produced by the glowing vapour of some compound, probably the oxide of the difficultly reducible metal, whereas, at the enormously high temperature of the intense electric spark, these compounds are split up, and the true spectrum is obtained, namely, the narrow bright lines. No such changes take place in the easily reducible metals, potassium, sodium, or lithium, which remain unaltered by change of temperature. In these experiments, a bead of the metallic salt on a platinum wire was placed between the platinum terminals, from which the spark of a powerful inductive coil could be passed, but in order to have a more intensely hot spark the coating of a Leyden jar was placed in communication with the terminals of the secondary current respectively. By this addition of static electricity, the intensity of the current was increased four-fold, and must have been beyond estimation.
By high temperature the cæsium spectrum has been so changed, that for number, colour and distinctness of its lines, it is the most beautiful of those of the alkaline and earthy metals, for besides its characteristic blue lines, it has six red and an orange-red line in the red part of its spectrum, a fine yellow line, and nine green lines, the last coinciding with Fraunhofer’s E. The thallium spectrum also acquires more lines when evaporated by electricity, for besides the remarkable green line in the green, it acquires a faint one in the orange, two of nearly equal intensity in the green, a third fainter, and a fifth in the blue.