Radium has been isolated in the metallic state (M. Curie and A. Debierne, 1910). The method used consisted in distilling under very pure hydrogen the amalgam of radium formed by the electrolysis of a chloride solution using a mercury cathode. One decigram only of salt was treated and consequently considerable difficulties were involved. The metal obtained melts at about 700°C, above which temperature it starts to volatilize. Is it very unstable in the air and decomposes water vigorously.
The radioactive properties of the metal are exactly the ones that can be forecast on the assumption that the radioactivity of the salts is an atomic property of the radium which is unaffected by the state of combination. It was of real importance to corroborate this point as misgivings had been voiced by those to whom the atomic hypothesis of radioactivity was still not evident.
Although radium has so far only been obtained in very small amounts, it is nevertheless true to say, in conclusion, that it is a perfectly defined and already well-studied chemical element.
Unfortunately, the same cannot be stated for polonium, for which nevertheless considerable effort has already been spent. The stumbling block here is the fact that the proportion of polonium in the mineral is about 5,000 times smaller than that of radium.
Before theoretical evidence was available from which to forecast this proportion, I had conducted several extremely laborious operations to concentrate polonium and in this way had secured products with very high activity without being able to arrive at definite results as in the case of radium. The difficulty is heightened by the fact that polonium disintegrates spontaneously, disappearing by half in a period of 140 days. We now know that radium has not an infinite life either, but the rate of disappearance is far less (it disappears by half in 2,000 years). With our facilities we can scarcely hope to determine the atomic weight of polonium because theory foresees that a rich mineral can contain only a few hundredths of a milligram per ton, but we can hope to observe its spectrum. The operation of concentrating polonium, as I shall point out later, is, moreover, a problem of great theoretical interest.
Recently, in collaboration with Debierne, I undertook to treat several tons of residues from uranium mineral with a view to preparing polonium. Initially conducted in the factory, then in the laboratory, this treatment finally yielded a few milligrams of substance about 50 times more active than an equal weight of pure radium. In the spectrum of the substance some new lines could be observed which appear attributable to polonium and of which the most important has the wavelength 4170.5 Å. According to the atomic hypothesis of radioactivity, the polonium spectrum should disappear at the same time as the activity and this fact can be confirmed experimentally,
I have so far considered radium and polonium only as chemical substances. I have shown how the fundamental hypothesis which states that radioactivity is an atomic property of the substance has led to the discovery of new chemical elements. I shall now describe how the scope of this hypothesis has been greatly enlarged by the considerations and experimental facts which resulted in establishing the theory of atomic radioactive transformations.
The starting-point of this theory must be sought in the considerations of the source of the energy involved in the phenomena of radioactivity. This energy becomes manifest as an emission of rays which produce thermal, electrical and light phenomena. As the emission occurs spontaneously without any known cause of excitation, various hypotheses have been advanced to account for the liberation of energy. One of the hypotheses put forward at the beginning of our research by Pierre Curie and myself consisted in assuming that the radiation is an emission of matter accompanied by a loss in weight of the active substances and that the energy is taken from the substance itself whose evolution is not yet completes and which undergoes an atomic transformation. This hypothesis, which at first could only be enunciated together with other equally valid theories, has attained dominant importance and finally asserted itself in our minds owing to a body of experimental evidence which substantiated it. This evidence is essentially the following: A series of radioactive phenomena exists in which radioactivity appears to be tied up to matter in an imponderable quantity, the radiation moreover not being permanent but disappearing more or less rapidly with time. Such are polonium, radioactive emanations and deposits of induced radioactivity.
It has been established moreover in certain cases that the radioactivity observed increases with time. This is what happens in the case of freshly prepared radium, of the emanation freshly introduced into the measuring apparatus, of thorium deprived of thorium X, etc.
A careful study of these phenomena has shown that a very satisfactory general explanation can be given by assuming that each time a decrease of radioactivity is observed there is a destruction of radioactive matter, and that each time an increase of activity is observed, there is a production of radioactive matter. The radiations which disappear and appear are, besides, of very varied nature and it is admitted that every kind of rays determined can serve to characterize a substance which is its source, and appears and disappears with it.
As radioactivity is in addition a property which is essentially atomic, the production or the destruction of a distinct type of radioactivity corresponds to a production or a destruction of atoms of a radioactive substance.
Finally, if it is supposed that radioactive energy is a phenomenon which is borrowed from atomic transformation, it can be deduced from this that every radioactive substance undergoes such a transformation, even though it appears to us to be invariable. Transformation in this case is only very slow and this is what takes place in the case of radium or uranium.
The theory I have just summarized is the work of Rutherford and Soddy, which they have called theory of atomic disintegration. By applying this theory it can be concluded that a primary radioactive substance such as radium undergoes a series of atomic transmutations by virtue of which the atom of radium gives birth to a train of atoms of smaller and smaller weights, since a stable state cannot be attained as long as the atom formed is radioactive. Stability can only be attained by inactive matter.
From this point of view one of the most brilliant triumphs of the theory is the prediction that the gas helium, always present in radioactive minerals, can represent one of the end-products of the evolution of radium, and that it is in the form of alpha rays that the helium atoms which are formed when radium atoms distintegrate are discharged. Now, the production of helium by radium has been proved by the experiments of Ramsay and Soddy, and it cannot now be contested that the perfectly defined chemical element, radium, gives rise to the formation of another equally defined element - helium. Moreover, the investigations done by Rutherford and his students have proved that the alpha particles emitted by radium with an electric charge are also to be found in the form of helium gas in the space where they have been recovered.
I must remark here that the bold interpretation of the relationship existing between radium and helium rests entirely upon the certitude that radium has the same claim to be a chemical element as have all the other known elements, and that there can be no question of regarding it to be a molecular combination of helium with another element. This shows how fundamental in these circumstances has been the work carried out to prove the chemical individuality of radium, and it can also be seen in what way the hypothesis of the atomic nature of radioactivity and the theory of radioactive transformations have led to the experimental discovery of a first clearly-established example of atomic transmutation. This is a fact the significance of which cannot escape anyone, and one which incontestably marks an epoch from the point of view of chemists.
Considerable work, guided by the theory of radioactive transformations, has led to approximately 30 new radioactive elements being envisaged, classified in 4 series according to the primary substance: these series are uranium, radium, thorium and actinium. The uranium and radium series can, in fact, be combined, for it seems to be proved that radium is a derivative of uranium. In the radium series the last known radioactive body is polonium, the production of which by radium is now a proven fact. It is likely that the actinium series is related to that of radium.
We have seen that helium gas is one of the products of radium distintegration. The helium atoms are detached from those of radium and its derivatives during the course of the transformation. It is supposed that after the departure of four atoms of helium, the radium atom yields one atom of polonium; the departure of a fifth helium atom determines the formation of an inactive body with an atomic weight believed to be equal to 206 (20 units below that of radium). According to Rutherford this final element is nothing more than lead, and this supposition is now being subjected to experimental verification in my laboratory. The production of helium from polonium has been directly proved by Debierne.
The relatively large amount of polonium prepared by Curie and Debierne has allowed an important study to be undertaken. This consists in counting a large number of alpha particles emitted by polonium and in collecting and measuring the corresponding volume of helium. Since each particle is a helium atom, the number of helium atoms is thus found which occupy a given volume and have a given weight. It can therefore allow us to deduce, in a general way, the number of molecules in a grammolecule. This number, known as Avogadro's constant, is of great importance. Experiments conducted on polonium have supplied a first value for this number, which is in good agreement with the values obtained by other methods. The enumeration of alpha particles is done by an electrometric method due to Rutherford; this method has been brought to perfection by means of a photographic recording apparatus.
Recent investigations have shown that potassium and rubidium emit a very feeble radiation, similar to the beta radiation of uranium and radium. We do not yet know whether we should regard these substances as true radioactive bodies, i.e. bodies in the process of transformation.
To conclude I should like to emphasize the nature of the new chemistry of radioactive bodies. Tons of material have to be treated in order to extract radium from the ore. The quantities of radium available in a laboratory are of the order of one milligram, or of a gram at the very most, this substance being worth 400,000 francs per gram. Very often material has been handled in which the presence of radium could not be detected by the balance, nor even by the spectroscope. And yet we have methods of measuring so perfect and so sensitive that we are able to know very exactly the small quantities of radium we are using. Radioactive analysis by electrometric methods allows us to calculate to within 1% a thousandth of a milligram of radium, and to detect the presence of 10-10 grams of radium diluted in a few grams of material. This method is the only one which could have led to the discovery of radium in view of the dilution of this substance in the ore. The sensitivity of the methods is still more striking in the case of radium emanation, which can be detected when the quantity present amounts, for example, to only 10-10 mm3. As the specific activity of a substance is, in the case of analogous radiations, approximately in inverse proportion to the average life, the result is that if the average life is very brief, the radioactive reaction can attain an unprecedented sensitivity. We are also accustomed to deal currently in the laboratory with substances the presence of which is only shown to us by their radioactive properties but which nevertheless we can determine, dissolve, reprecipitate from their solutions and deposit electrolytically. This means that we have here an entirely separate kind of chemistry for which the current tool we use is the electrometer, not the balance, and which we might well call the chemistry of the imponderable.
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الأحد نوفمبر 30, 2014 1:29 am من طرف نجمة الجنوب
