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ELEMENTS, NEW AND CHEMICALLY NEW 127
Again, the first-fruits of the discovery of radioactivity were the recognition of the new elements polonium, radium, and actinium by their unique radioactive character in the first place. Then, in the case of radium, its claim to the title of element was confirmed, first by its exhibiting a unique spectrum, then' by its possession of unique chemical character and atomic weight and by its occupying a vacant place in the periodic table. The emanations, next, as occupying a place in the family of argon gases, were easily characterised, and for the radium emanation unique spectrum was proved. Its origin from radium by loss of one a-particle gives the atomic weight as 222, which agrees with determinations
of its density and rate of diffusion. The chemical · characters of polonium and of actinium are different
from those of the elements they most closely resemble. Polonium, or radium-F, by its close chemical analogy to both bismuth and tellurium, was characterised as an element of the sulphur family occupying the vacant place contiguous to bismuth. Actinium, by its resemblance in chemical character to the rare earths, and especially to lanthanum, although capable of being concentrated fractionally from that element, was reasonably supposed to occupy the vacant place in Group III, between radium and thorium. As will later appear evident, both these elements in due course may be expected to show unique spectra.
Further progress in the elucidation of the chemical character of successive products then underwent an abrupt and, at first, very puzzling change of direction. As member after member in the series was distinguished and characterised by its unique radioactive character, by its disintegration in definite and characteristic ways at definite and characteristic rates, no further chemically new elements were discovered. Unique radioactive character does not
always, as it did with radium, imply unique chemical and spectroscopic character. The new members resembled known elements in chemical character so closely that they could not be separated from them by chemical analysis, although sharply differentiated from them by the radioactive properties. Radiolead, or radium-D, cannot be separated from the lead which, being a product of uranium, accompanies it always in uranium minerals. Ionium, the direct parent of radium, cannot be separated from thorium ; but the most instructive case, historically, which shows well how the new method of radioactive analysis serves to distinguish different elements, where chemical analysis fails, was the case of radiothorium.
CHEMICALLY NON-SEPARABLE ELEMENTS. Ramsay and Hahn, in the course of working up a large quantity of thorianite for radium, observed in fractionating the radium from the barium in the usual way that the activity of the material concentrated at both ends of the fractionation. The activity accumulating in the more soluble fractions was due to a new product, which they termed radiothorium. It produces thorium-X, the thorium emanation, etc., in successive changes. Naturally enough, they thought they had separated radiothorium by chemical processes from thorium, but they had not, for that, as we know, is quite impossible. Then Hahn found along with the other end fraction, containing the radium, a further new product, mesothorium, which is intermediate between thorium and radiothorium. The radiothorium they had separated from thorianite was not that present in the mineral when they started, but that which had re-formed from the mesothorium after it had been separated from the thorium in the mineral. Could any more elegant extension, not
merely of knowledge, but of the means of obtaining knowledge, be imagined? Two different elements. thorium and radiothorium, which on account of their chemical resemblance could not be individually recognised, and in the original interpretation of the thorium disintegration series were taken as one, became individually knowable, because the latter is the product of the former through the intermediary of a third member, mesothorium, possessing chemical properties totally unlike either. Radioactive change thus became the means of a new analysis of matter, for which there is no counterpart outside the radioelements.
In turn, mesothorium suffered analysis into two successive products, mesothorium-I and -2, the first distinguished by long period of life and a rayless disintegration into the second, which has a short life and gives powerful ß- and y-radiation in its change into radiothorium.
I then found that mesothorium-I was chemically non-separable from radium, a discovery also made by Marckwald at the same time, and in 1911 I pointed out that in an a-ray change, such as ionium into radium, radium into emanation, thorium into mesothorium-I, and other cases, the expulsion of the a-particle causes the radio-element to shift its place in the periodic table by two places in the direction of diminishing mass and diminishing valency, whereas in successive changes in which a-particles are not expelled, it frequently reverts to its former position, as, for example, radiothorium from mesothorium and lead from radiolead.
To those actually engaged in the task of trying to separate the successive products of radioactive change by chemical analysis, it soon became clear that the chemical resemblances disclosed between certain of the members was such as to amount to
chemical identity. The most obstinate cases of similarity previously known, among the rare earths, for example, cannot be compared with them. In all cases, radioactive methods afford the most delicate means for detecting the least alteration in the concentration of the constituents, and the most prolonged and careful attempts fail to produce a detectable separation.
At my request, Fleck undertook in my laboratory a systematic chemical examination of all the members of the series still imperfectly characterised, from the point of view of first finding which known element they most resembled and then finding whether or not they could be separated from that element. His researches were the means of finally unmasking the extreme simplicity and profound theoretical significance of the process of radioactive change. All the members of the series so far chemically uncharacterised he found to be chemically non-separable from one or other of the known elements, mesothorium-2 from actinium, radium-A from polonium, the three B-members and radium-D from lead, the three C-members and radium-E from bismuth, actinium-D and thorium-D from thallium.
RADIOACTIVE CHANGE AND THE PERIODIC LAW.
In February, 1913, K. Fajans in Germany, from electrochemical evidence, and in this country A. S. Russell and I, independently, from Fleck's work, pointed out the complete generalisation which connects chemical character and radioactive change. In addition to the shift of two places in the periodic table caused by the expulsion of the a-particle, it was now clear that the expulsion of the B-particle caused a shift of one place in the opposite direction. Since the a-particle carries two atomic charges of positive
ISOTOPES AND HETEROTOPES
electricity and the B-particle one atomic charge of negative electricity, the successive places in the periodic table must thus correspond with unit difference of charge in the atomic structure, a conclusion reached later for the whole periodic table, as far as aluminium, as the result of Moseley's investigations on the frequency of Barkla's characteristic X-radiations of the elements.
The non-separable elements, with identical chemical character, on this scheme were found all to occupy the same place in the periodic table, and on this account I named them isotopes. Conversely, the different elements recognised by chemical analysis should be termed "heterotopes,” that is, substances occupying separate places in the periodic table, but themselves mixtures, actually proved or potential, of different isotopes, not necessarily homogeneous as regards atomic weight and radioactive character, but homogeneous as regards chemical and spectroscopic character, and also physical character, so far as that is not directly dependent on atomic mass.
SPECTRA OF ISOTOPES.
As regards the spectrum, the first indication that chemically non-separable elements probably possessed identical spectra arose out of the failure of Russell and Rossi and of Exner and Haschek in 1912 to detect any lines other than those of thorium in the spectrum of ionium-thorium preparations that might reasonably be supposed to contain an appreciable, if not considerable, percentage of ionium. The work of Hönigschmid on the atomic weight of ionium-thorium preparations has fully confirmed this view. The isotopes of lead of different atomic weight separated from uranium and thorium minerals have been found to possess