was calculated to give, when combined, a mixture of a definite percentage composition by weight (this being more easily obtainable than a percentage composition by volume).
The quantities generally chosen were 10, 5, 1, and 0·1 per cent.
In a few cases, with metals known to have very delicate spectral reactions, a mixture of 0·01 per cent, was prepared.
Observations were then made of the spectrum of each specimen, and the result was recorded in maps in the following manner: First, the pure spectrum of the smallest constituent was observed, and the lines laid down from Thalén's map.
The series thus mapped was as follows:
| Tin | + Cadmium, | percentages of | Cd 10, 5, | 1 | , | 0 | ·15 |
| Lead | + Zinc, | " | Zn 10, 5, | 1 | , | 0 | ·1 |
| Lead | + Magnesium, | " | Mg 10, 1, | 0 | ·1, | 0 | ·01 |
The observations showed that the lines of the smallest constituent disappeared as the quantity got less. Although we had here the germs of a quantitative spectrum analysis, the germs only were present, because from the existence of several "critical points," and great variations due to other causes, the results obtained were not constant.
In a subsequent research on the gold-copper alloys used in the coinage, Mr. Roberts, the Chemist of the Mint, and myself were able to show that the shortening in the length of the lines by reduced quantity was such a definite physical effect following upon reduced quantity, that a difference of 110000 part of copper in gold could be detected.
We are now in possession of the facts utilized in the work which has led up to the subject discussed in the present paper.
They have been utilized along two perfectly distinct lines of thought:
(1) They have been used in an attempt to enable us to produce a spectrum of a substance free from lines due to the impurities which are almost always present.
(2) They have been used to indicate the existence and amount of dissociation when acknowledged compounds have been submitted to the action of different and increasing temperatures.
I will deal with (1) first.
The elimination of impurity lines is conducted as follows: The spectrum of the element is first confronted with the spectra of the substances most likely to be present to impurities. This is most conveniently done by photographing the spectra on the same plate one above the other, so that common lines are continuous.
The retention or rejection of lines coincident in two or more spectra is determined by observing in which spectrum the line is thickest; where several elements are mapped at once, all their spectra are confronted on the same plate, as by this means the presence of one of the substances as an impurity in the others can be at once detected.
