constant for slow speeds but increases as the speed of light is approached. Now radium emits some electrons at a velocity comparable with the velocity of light, and presumably these electrons were in rapid motion in the atom before their expulsion. It might thus be possible that the ratio for radium would differ from that for ordinary matter. The pendulum method was used, and the radium was enclosed in a small light tube suspended by a silk fibre. Within the limit of experimental error the ratio of weight to mass was found to be the same as for ordinary matter, so that we may conclude that the number of electrons moving with a velocity approaching that of light is small compared with the total number present.
=266. Total emission of energy from the radio-element.= It has been shown that 1 gram of radium emits energy at the rate of 100 gram-calories per hour or 876,000 gram-calories per year. If 1 gram of radium in radio-active equilibrium be set apart, its radio-activity and consequent heat emission is given at a time t by
$$ qe^{–λt} $$,
where λ is the constant of decay of activity of radium and of the initial heating effect; the total heat emission from 1 gram of radium is given by
$$ \int₀^{\infty} qe^{–λt} dt = \frac {q} {λ} $$ .
Now on the estimate of the life of radium given in section 261 the value of λ is ¹⁄₁₈₅₀ when 1 year is taken as the unit of time. The total heat emission from 1 gram of radium during its life is thus 1·6 × 10⁹ gram-calories. The heat emitted in the union of hydrogen and oxygen to form 1 gram of water is about 4 × 10³ gram-calories, and in this reaction more heat is given out for equal weights than in any other chemical reaction known. It is thus seen that the total energy emitted from 1 gram of radium during its changes is about one million times greater than in any known molecular change. That matter is able, under special conditions, to emit an enormous amount of energy, is well exemplified by the case of the radium emanation. Calculations of the amount of this energy have already been given in section 249.
Since the other radio-elements only differ from radium in the slowness of their change, the total heat emission from uranium and thorium must be of a similar high order of magnitude. There is thus reason to believe that there is an enormous store of latent energy resident in the atoms of the radio-elements. This store of energy could not have been recognized if the atoms had not been undergoing a slow process of disintegration. The energy emitted in radio-active changes is derived from the internal energy of the atoms. The emission of this energy does not disobey the law of the conservation of energy, for it is only necessary to suppose that, when the radio-active changes have ceased, the energy stored up in the atoms of the final products is less than that of the original atoms of the radio-elements. The difference between the energy originally possessed by the matter which has undergone the change, and the final inactive products which arise, is a measure of the total amount of energy released.
There seems to be every reason to suppose that the atomic energy of all the elements is of a similar high order of magnitude. With the exception of their high atomic weights, the radio-elements do not possess any special chemical characteristics which differentiate them from the inactive elements. The existence of a latent store of energy in the atoms is a necessary consequence of the modern view developed by J. J. Thomson, Larmor, and Lorentz, of regarding the atom as a complicated structure consisting of charged parts in rapid oscillatory or orbital motion in regard to one another. The energy may be partly kinetic and partly potential, but the mere concentration of the charged particles, which probably constitute the atom, in itself implies a large store of energy in the atom, in comparison with which the energy emitted during the changes of radium is insignificant.
The existence of this store of latent energy does not ordinarily manifest itself, since the atoms cannot be broken up into simpler forms by the physical or chemical agencies at our disposal. Its existence at once explains the failure of chemistry to transform the atoms, and also accounts for the rate of change of the radio-active processes being independent of all external agencies. It has not so far been found possible to alter in any way the rate of emission of energy from the radio-elements. If it should ever be found possible to control at will the rate of disintegration of the radio-elements, an enormous amount of energy could be obtained from a small quantity of matter.
=267. Production of helium from radium and the radium emanation.= Since the final products, resulting from a disintegration of the radio-elements, are not radio-active, they should in the course of geologic ages collect in some quantity, and should always be found associated with the radio-elements. Now the inactive products resulting from the radio-active changes are the α particles expelled at each stage, and the final inactive product or products which remain, when the process of disintegration can no longer be traced by the property of radio-activity.
Pitchblende, in which the radio-elements are mostly found, contains in small quantity a large proportion of all the known elements. In searching for a possible disintegration product common to all the radio-elements, the presence of helium in the radio-active minerals is noteworthy; for helium is only found in the radio-active minerals, and is an invariable companion of the radio-elements. Moreover, the presence in minerals of a light, inert gas like helium had always been a matter of surprise. The production by radium and thorium of the radio-active emanations, which behave like chemically inert gases of the helium-argon family, suggested the possibility that one of the final inactive products of the disintegration of the radio-elements might prove to be a chemically inert gas. The later discovery of the material nature of the α rays added weight to the suggestion; for the measurement of the ratio e/m of the α particle indicated that if the α particle consisted of any known kind of matter, it must either be hydrogen or helium. For these reasons, it was suggested in 1902 by Rutherford and Soddy that helium might be a product of the disintegration of the radio-elements.
Sir William Ramsay and Mr Soddy in 1903 undertook an investigation of the radium emanation, with the purpose of seeing if it were possible to obtain any spectroscopic evidence of the presence of a new substance. First of all, they exposed the emanation to very drastic treatment (section 158), and confirmed and extended the results previously noted by Rutherford and Soddy that the emanation behaved like a chemically inert gas, and in this respect possessed properties analogous to the gases of the helium-argon group.
On obtaining 30 milligrams of pure radium bromide (prepared about three months previously) Ramsay and Soddy examined the gases, liberated by solution of the radium bromide in water, for the presence of helium. A considerable quantity of hydrogen and oxygen was released by the solution (see section 124). The hydrogen and oxygen were removed by passing the liberated gases over a red-hot spiral of partially oxidized copper-wire and the resulting water vapour was absorbed in a phosphorus pentoxide tube.
The gas was then passed into a small vacuum tube which was in connection with a small =U= tube. By placing the =U= tube in liquid air, most of the emanation present was condensed, and also most of the CO₂ present in the gas. On examining the spectrum of the gas in the vacuum tube, the characteristic line D₃ of helium was observed.
This experiment was repeated with 30 milligrams of radium bromide about four months old, lent for the purpose by the writer. The emanation and CO₂ were removed by passing them through a =U= tube immersed in liquid air. A practically complete spectrum of helium was observed, including the lines of wave-lengths 6677, 5876, 5016, 4972, 4713 and 4472. There were also present three other lines of wave-lengths about 6180, 5695, 5455 which have not yet been identified.
In later experiments, the emanation from 50 milligrams of the radium bromide was conveyed with oxygen into a small =U= tube, cooled in liquid air, in which the emanation was condensed. Fresh oxygen was added, and the =U= tube again pumped out. The small vacuum tube, connected with the =U= tube, showed at first no helium lines when the liquid air was removed. The spectrum obtained was a new one, and Ramsay and Soddy considered it to be probably that of the emanation itself. After allowing the emanation tube to stand for four days, the helium spectrum appeared with all the characteristic lines, and in addition, three new lines present in the helium obtained by solution of the radium. These results have since been confirmed. The experiments, which have led to such striking and important results, were by no means easy of performance, for the quantity of helium and of emanation released from 50 mgrs. of radium bromide is extremely small. It was necessary, in all cases, to remove almost completely the other gases, which were present in sufficient quantity to mask the spectrum of the substance under examination. The success of the experiments has been largely due to the application, to this investigation, of the refined methods of gas analysis, previously employed by Sir William Ramsay with so much skill in the separation of the rare gases xenon and krypton, which exist in minute proportions in the atmosphere. The fact that the helium spectrum was not present at first, but appeared after the emanation had remained in the tube for some days, shows that the helium must have been produced from the emanation. The emanation cannot be helium itself, for, in the first place, helium is not radio-active, and in the second place, the helium spectrum was not present at first, when the quantity of emanation in the tube was at its maximum. Moreover, the diffusion experiments, already discussed, point to the conclusion that the emanation is of high molecular weight. There can thus be no doubt that the helium is derived from the emanation of radium in consequence of changes of some kind occurring in it.
These results were confirmed later by other observers. Curie and Dewar performed the following experiment: A weight of about ·42 gr. of radium bromide was placed in a quartz tube, and the tube exhausted until no further gas came off. The radium was then heated to fusion, about 2·6 c.c. of gas being liberated in the process. The tube was then sealed, and some weeks afterwards the spectrum of the gas liberated in the tube by the radium was examined by Deslandres and found to give the entire spectrum of helium. The gas, liberated during the initial heating of the radium, was collected and found to contain a large amount of emanation, although the gas had been passed through two tubes immersed in liquid air. The tube containing these gases was very luminous and rapidly turned violet, while more than half of the gases was absorbed. The spectrum of the phosphorescent light was found to be discontinuous, consisting of three nitrogen bands. No sign of the helium spectrum was observed, although helium must have been present.
Himstedt and Meyer placed 50 mgrs. of radium bromide in a =U= tube connected with a small vacuum tube. The tube was carefully exhausted and then sealed off. The spectrum of hydrogen and carbon dioxide alone was observed for three months, but after four months the red, yellow, green and blue lines of the helium spectrum were visible. The slow appearance of the helium spectrum was probably due to the presence in the tube of a considerable quantity of hydrogen. In another experiment, some radium sulphate which had been heated to a bright red heat in a quartz tube was connected with a small vacuum tube. After three weeks, some of the lines of helium were clearly seen, and increased in brightness with time.
=268. Connection between helium and the α particles=. The appearance of helium in a tube containing the radium emanation may indicate either that the helium is one of the final products, which appear at the end of the series of radio-active changes, or that the helium is in reality the expelled α particle. The evidence at present points to the latter as being the more probable explanation. In the first place, the emanation diffuses like a gas of heavy molecular weight, and it appears probable that after the expulsion of a few α particles, the atomic weight of the final product is comparable with that of the emanation. On the other hand, the value of e/m determined for the projected α particle points to the conclusion that, if it consists of any known kind of matter, it is either hydrogen or helium.
There has been a tendency to assume that the helium produced from the radium emanation is the last transformation product of that substance. The evidence, however, does not support this view. We have seen that the emanation, after the initial rapid changes, is transformed very slowly. If the helium were the final product, the amount present in the emanation tube after a few days or weeks would be insignificant, since the product radium D intervenes, which takes 40 years to be half transformed. Since the helium cannot be the final product of the series of changes, and since all the other products are radio-active, and almost certainly of high atomic weight, it is difficult to see what position the helium atom occupies in the scheme of transformation, unless it be the α particle expelled during the successive changes.
It is a matter of great difficulty to settle definitely whether the α particle is a projected helium atom or not. On account of the very small deflection of the α rays in an electric field, and the complex nature of the α radiation from radium, an accurate determination of the value e/m for the α particle is beset with difficulties.
It may be possible to settle the question by accurate measurements of the volume of gas in a tube, filled originally with the radium emanation. Since the emanation itself, and two of the rapidly changing products which result from it, emit α particles, the final volume of the α particles, if they can exist in the gaseous state, would be three times the volume of the emanation. Ramsay and Soddy (section 172) have made experiments of this kind, but the results obtained were very contradictory, depending upon the kind of glass employed. In one case, the volume of the residual gases shrank almost to zero, in another the initial volume increased to about ten times its initial value. In the latter experiment a brilliant spectrum of helium was observed in the residual gas. This difference of behaviour is probably due to different degrees of absorption of helium by the glass tubes.
If the α particles are helium atoms, we may expect that a large proportion of the helium, which is produced in a tube containing the radium emanation, will be buried in the wall of the glass tube; for the α particles are projected with sufficient velocity to penetrate some distance into the glass. This helium may either remain in the glass, or in some cases rapidly diffuse out again. In any case, a fraction of the helium would be liberated when an intense electric discharge is passed through the tube. Ramsay and Soddy have in some instances observed that a slight amount of helium is liberated on heating the walls of the tube in which the emanation had been stored for some time.
The volume of helium produced per year by 1 gram of radium can easily be calculated on the assumption that the α particle is in reality a helium atom.
It has been shown that 2·5 × 10¹¹ α particles are projected per second from 1 gram of radium. Since there are 3·6 × 10¹⁹ molecules in one cubic centimetre of any gas at standard pressure and temperature, the volume of the α particles released per second is 7 × 10⁻⁹ c.c. and per year 0·24 c.c. It has already been pointed out that, on this hypothesis, the volume of helium released by the emanation is three times the volume of the latter. The amount of helium to be obtained from the emanation released from 1 gram of radium in radio-active equilibrium is thus about 3 cubic mms.
Ramsay and Soddy have tried to estimate experimentally the probable volume of helium produced per second by one gram of radium. The helium, obtained from 50 mgrs. of radium bromide, which had been kept in solution in a closed vessel for 60 days, was introduced into a vacuum tube. Another similar tube was placed in series with it, and the amount of the helium in the latter adjusted until on passing a discharge through the two tubes in series the helium lines in each tube were of about the same brightness. In this way they calculated that the amount of helium present was 0·1 cubic mm. On this estimate, the amount of helium produced per year per gram of radium is about 20 cubic mms. We have seen that the calculated amount is about 240 cubic mms., on the assumption that the α particle is a helium atom. Ramsay and Soddy consider that the presence of argon in one of the tubes may have seriously interfered with the correctness of the estimation. On account of the great uncertainty attaching to estimates of the above character, the value deduced by Ramsay and Soddy does not exclude the probability that the calculated volume may be of the right order of magnitude.
In order to explain the presence of helium in radium on ordinary chemical lines, it has been suggested that radium is not a true element, but a molecular compound of helium with some substance known or unknown. The helium compound gradually breaks down, giving rise to the helium observed. It is at once obvious that this postulated helium compound is of a character entirely different from that of any other compound previously observed in chemistry. Weight for weight, it emits during its change an amount of energy at least one million times greater than any molecular compound known (see section 249). In addition, it must be supposed that the rate of breaking up of the helium compound is independent of great ranges of temperature—a result never before observed in any molecular change. The helium compound in its breaking up must give rise to the peculiar radiations and also pass through the successive radio-active changes observed in radium.
Thus in order to explain the production of helium and radio-activity on this view, a unique kind of molecule must be postulated—a molecule, in fact, which is endowed with every single property which on the disintegration theory is ascribed to the atom of the radio-elements. On the other hand, radium as far as it has been examined, has fulfilled every test required for an element. It has a well-marked and characteristic spectrum, and there is no reason to suppose that it is not an element in the ordinarily accepted sense of the term.
On the theory that the radio-elements are undergoing atomic disintegration, the helium must be considered to be a constituent of the radium atom, or, in other words, the radium atom is built up of parts, one of which, at least, is the atom of helium. The theory that the heavy atoms are all built up of some simple fundamental unit of matter or protyle has been advanced at various times by many prominent chemists and physicists. Prout’s hypothesis that all elements are built up out of hydrogen is an example of this point of view of regarding the subject.
On the disintegration theory, the changes occurring in the radio-atoms involve an actual transformation of the atoms through successive changes. This change is so slow in uranium and thorium that at least a million years would be required before the amount of change could be measured by the balance. In radium it is a million times faster, but even in this case it is doubtful whether any appreciable change would have been observed by ordinary chemical methods for many years had not the possibility of such a change been suggested from other lines of evidence.
The similarity of the α particles from the different radio-elements indicates that they consist of expelled particles of the same kind. On this view, helium should be produced by each of the radio-elements. Its presence in minerals containing thorium, for example in monazite sand and the Ceylon mineral described by Ramsay, indicates that helium may be a product of thorium as well as of radium. Strutt has recently suggested that most of the helium observed in radio-active minerals may be a decomposition product of thorium rather than of uranium and radium; for he finds that minerals rich in helium always contain thorium, while many uranium minerals nearly free from thorium contain little helium. The evidence in support of this view is, however, not altogether satisfactory, for some of the uranium minerals in question are secondary uranium minerals (see Appendix B), deposited by the action of water or other agencies at a comparatively late date, and are also, in many cases, highly emanating, and consequently could not be expected to retain more than a fraction of the helium produced in them.
Taking the view that the α particles are projected helium atoms, we must regard the atoms of the radio-elements as compounds of some known or unknown substance with helium. These compounds break up spontaneously, and at a very slow rate even in the case of radium. The disintegration takes place in successive stages, and at most of the stages a helium atom is projected with great velocity. This disintegration is accompanied by an enormous emission of energy. The liberation of such a large amount of energy in the radio-active changes at once explains the constancy of the rate of change under the action of any of the physical and chemical agencies at our command. On this view, uranium, thorium and radium are in reality compounds of helium. The helium, however, is held in such strong combination that the compound cannot be broken up by chemical or physical forces, and, in consequence, these bodies behave as chemical elements in the ordinary accepted chemical sense.
It appears not unlikely that many of the so-called chemical elements may prove to be compounds of helium, or, in other words, that the helium atom is one of the secondary units with which the heavier atoms are built up. In this connection it is of interest to note that many of the elements differ in their atomic weight by four—the atomic weight of helium.
If the α particle is a helium atom, at least three α particles must be expelled from uranium (238·5) to reduce its atomic weight to that of radium (225). It is known that five α particles are expelled from radium during its successive transformations. This would make the atomic weight of the final residue 225 − 20 = 205. This is very nearly the atomic weight of lead, 206·5. I have, for some time, considered it probable that lead is the end or final product of radium. The same suggestion has recently been made by Boltwood. This point of view is supported by the fact that lead is always found in small quantity in all uranium minerals, and that the relative proportions of lead and helium in the radio-active minerals are about the same as would be expected if lead and helium were both decomposition products of radium. Dr Boltwood has drawn my attention to the fact that the proportion of lead in many radio-active minerals varies with the content of helium. A mineral rich in helium in nearly all cases contains more lead than a mineral poor in helium. This cannot be considered, at present, more than a speculation, but the facts as they stand are very suggestive.
=269. Age of radio-active minerals.= Helium is only found in the radio-active minerals, and this fact, taken in conjunction with the liberation of helium by radium, indicates that the helium must have been produced as a result of the transformation of radium and the other radio-active substances contained in the minerals. Now in a mineral about half the helium is, in many cases, released by heat and the residue by solution. It seems probable that the helium produced throughout the mass of the mineral is mechanically imprisoned in it. Moss found that, by grinding pitchblende in vacuo, helium is evolved, apparently showing that the helium exists in cavities of the mineral. Travers has suggested that, since helium is liberated on heating, the effect may be due to the heat generated by grinding. The escape of the helium from the heated mineral is probably connected with the fact observed by Jaquerod that helium passes through the walls of a quartz tube, heated above 500° C. The substance of the mineral probably possesses a similar property. Travers considers that helium is present in the mineral in a state of supersaturated solid solution, but the facts are equally well explained by assuming that the helium is mechanically imprisoned in the mass of the mineral.
The sudden rise of temperature observed in the mineral fergusonite, at the time the helium is released, has been found to have nothing to do with the presence of helium, for it also takes place in minerals not containing helium. The old view that helium was in a state of chemical combination with the mineral must be abandoned in the light of these more recent experiments.
Since the helium is only released from some minerals by the action of high temperatures and solution, it appears probable that a large proportion of the helium found in the minerals is unable to escape under normal conditions. Thus if the rate of production of helium by the radio-active substance were definitely known, it should be possible to calculate the age of the mineral by observing the volume of helium liberated from it by solution.
In the absence of such definite information, an approximate calculation will be made to indicate the order of magnitude of the time that has elapsed since the mineral was formed or was at a temperature low enough to prevent the escape of the helium.
Let us take, for example, the mineral fergusonite, which was found by Ramsay and Travers to evolve 1·81 c.c. of helium. The fergusonite contained about 7 per cent. of uranium. Now uranium in old minerals probably contains about 8 × 10⁻⁷ of its weight of radium (see section 262). One gram of the mineral thus contained about 5·6 × 10⁻⁸ grams of radium. Now if the α particle is helium, it has been shown that 1 gram of radium produces 0·24 c.c. of helium per year. The volume of helium produced per year in 1 gram of fergusonite is thus 1·3 × 10⁻⁸ c.c. Assuming that the rate of production of helium has been uniform, the time required to produce 1·81 c.c. per gram is about 140 million years. If the calculated rate of production of helium by radium is an over-estimate, the time is correspondingly lengthened.
I think that, when the constants required for these calculations are more definitely fixed, this method will probably give fairly trustworthy information as to the probable age of some of the radio-active minerals of the earth’s crust, and indirectly as to the age of the strata in which they are found.
In this connection it is of interest to note that Ramsay found that a Ceylon mineral, thorianite, contained as much as 9·5 c.c. of helium per gram. According to the analysis by Dunstan, this mineral contains about 76 per cent. of thorium and 12 per cent. of uranium. The unusually large amount of helium evolved from this mineral would indicate that it was formed at an earlier date than the fergusonite previously considered.
=270. Possible causes of disintegration.= In order to explain the phenomena of radio-activity, it has been supposed that a certain small fraction of the radio-atoms undergoes disintegration per second, but no assumptions have been made as to the cause which produces the instability and consequent disintegration. The instability of the atoms may be supposed to be brought about either by the action of external forces or by that of forces inherent in the atoms themselves. It is conceivable, for example, that the application of some slight external force might cause instability and consequent disintegration, accompanied by the liberation of a large amount of energy, on the same principle that a detonator is necessary to start some explosives. It has been shown that the number of atoms of any radio-active product which break up per second is always proportional to the number present. This law of change does not throw any light on the question, for it would be expected equally on either hypothesis. It has not been found possible to alter the rate of change of any product by the application of any known physical or chemical forces, unless possibly it is assumed that the force of gravitation which is not under our control may influence in some way the stability of the radio-atoms.
It seems likely therefore that the cause of the disruption of the atoms of the radio-elements and their products resides in the atoms themselves. According to the modern views of the constitution of the atom, it is not so much a matter of surprise that some atoms disintegrate as that the atoms of the elements are so permanent as they appear to be. In accordance with the hypothesis of J. J. Thomson, it may be supposed that the atoms consist of a number of small positively and negatively charged particles in rapid internal movement, and held in equilibrium by their mutual forces. In a complex atom, where the possible variations in the relative motion of the parts are very great, the atom may arrive at such a phase that one part acquires sufficient kinetic energy to escape from the system, or that the constraining forces are momentarily neutralised, so that the part escapes from the system with the velocity possessed by it at the instant of its release.
Sir Oliver Lodge has advanced the view that the instability of the atom may be a result of radiation of energy by the atom. Larmor has shown that an electron, subject to acceleration, radiates energy at a rate proportional to the square of its acceleration. An electron moving uniformly in a straight line does not radiate energy, but an electron, constrained to move in a circular orbit with constant velocity, is a powerful radiator, for in such a case the electron is continuously accelerated towards the centre. Lodge considered the simple case of a negatively charged electron revolving round an atom of mass relatively large but having an equal positive charge and held in equilibrium by electrical forces. This system will radiate energy, and, since the radiation of energy is equivalent to motion in a resisting medium, the particle tends to move towards the centre, and its speed consequently increases. The rate of radiation of energy will increase rapidly with the speed of the electron. When the speed of the electron becomes very nearly equal to the velocity of light, according to Lodge, another effect supervenes. It has been shown (section 82) that the apparent mass of an electron increases very rapidly as the speed of light is approached, and is theoretically infinite at the speed of light. There will be at this stage a sudden increase of the mass of the revolving atom, and, on the supposition that this stage can be reached, a consequent disturbance of the balance of forces holding the system together. Lodge considers it probable that, under these conditions, the parts of the system will break asunder and escape from the sphere of one another’s influence.
It seems probable that the primary cause of the disintegration of the atom must be looked for in the loss of energy of the atomic system due to electromagnetic radiation (section 52). Larmor has shown that the condition to be fulfilled in order that a system of rapidly moving electrons may persist without loss of energy is that the vector sum of the accelerations towards the centre should be permanently zero. While a single electron moving in a circular orbit is a powerful radiator of energy, it is remarkable how rapidly the radiation of energy diminishes if several electrons are revolving in a ring. This has recently been shown by J. J. Thomson, who examined mathematically the case of a system of negatively electrified corpuscles, situated at equal intervals round the circumference of a circle, and rotating in one plane with uniform velocity round its centre. For example, he found that the radiation from a group of six particles moving with a velocity of ⅒ of the velocity of light is less than one-millionth part of the radiation from a single particle describing the same orbit with the same velocity. When the velocity is ¹⁄₁₀₀ of that of light the amount of radiation is only 10⁻¹⁶ that of a single particle moving with the same velocity in the same orbit.
Results of this kind indicate that an atom consisting of a large number of revolving electrons may radiate energy extremely slowly, and yet, finally, this minute but continuous drain of energy from the atom must result either in a rearrangement of its component parts into a new system, or of an expulsion of electrons or groups of electrons from the atom.
Simple models of atoms to imitate the behaviour of polonium in shooting out α particles, and of radium in shooting out β particles have been discussed by Lord Kelvin. It is possible to devise certain stable arrangements of the positively and negatively electrified particles, supposed to constitute an atom, which, on the application of some disturbing force, break up with the expulsion of a part of the system with great velocity.
J. J. Thomson has mathematically investigated the possible stable arrangements of a number of electrons moving about in a sphere of uniform positive electrification. The properties of such a model atom are very striking, and indirectly suggest a possible explanation of the periodic law in chemistry. He has shown that the electrons, if in one plane, arrange themselves in a number of concentric rings; and generally, if they are not constrained to move in one plane, in a number of concentric shells like the coats of an onion.
The mathematical problem is much simplified if the electrons are supposed to rotate in rings in one plane, the electrons in each ring being arranged at equal angular intervals. The ways in which the number of electrons group themselves, for numbers ranging from 60 to 5 at intervals of 5, are shown in the following table:—
Number 60 55 50 45 40 35 of electrons
Number in 20 19 18 17 16 16 successive rings
16 16 15 14 13 12
13 12 11 10 8 6
8 7 5 4 3 1
3 1 1
Number 30 25 20 15 10 5 of electrons
Number in 15 13 12 10 8 5 successive rings
10 9 7 5 2
5 3 1
In the next table is given the possible series of arrangements of electrons which can have an outer ring of 20:—
Number 59 60 61 62 63 64 65 66 67 of electrons
Number in 20 20 20 20 20 20 20 20 20 successive rings
16 16 16 17 17 17 17 17 17
13 13 13 13 13 13 14 14 15
8 8 9 9 10 10 10 10 10
2 3 3 3 3 4 4 5 5
The smallest number of electrons which can have an outer ring of 20 is 59, while 67 is the greatest.
The various arrangements of electrons can be classified into families, in which the groupings of the electrons have certain features in common. Thus the group of 60 electrons consists of the same arrangement of electrons as the group of 40 with the addition of an outer ring of 20 electrons; the group of 40 is the same as the group of 24 with an additional ring outside; and the group of 24 in turn is the same as the group of 11 with an extra ring. A series of model atoms may be formed in this way, in which each atom is derived from the preceding member by an additional ring of electrons. Such atoms would be expected to possess many properties in common, and would correspond to the elements in the same vertical column of the periodic table of Mendeléef.
Different arrangements of electrons vary widely in stability. Some may acquire an extra electron or two and yet remain stable, others readily lose an electron without disturbing their stability. The former would correspond to an electro-negative atom, the latter to an electro-positive.
Certain arrangements of electrons are stable if the electrons move with an angular velocity greater than a certain value, but become unstable when the velocity falls below this value. Four electrons in motion, for example, are stable in one plane, but when the velocity falls below a certain critical value, the system is unstable, and the electrons tend to arrange themselves at the corners of a regular tetrahedron. J. J. Thomson (loc. cit.) applies this property to explain why an atom of radio-active matter breaks up, as follows:—
“Consider now the properties of an atom containing a system of corpuscles (electrons) of this kind. Suppose the corpuscles were originally moving with velocities far exceeding the critical velocity; in consequence of the radiation from the moving corpuscles, their velocity will slowly—very slowly—diminish; when, after a long interval, the velocity reaches the critical velocity, there will be what is equivalent to an explosion of the corpuscles, the corpuscles will move far away from their original position, their potential energy will decrease, while their kinetic energy will increase. The kinetic energy gained in this way might be sufficient to carry the system out of the atom, and we should have, as in the case of radium, a part of the atom shot off. In consequence of the very slow dissipation of energy by radiation the life of the atom would be very long. We have taken the case of the four corpuscles as the type of a system which, like a top, requires for its stability a certain amount of rotation. Any system possessing this property would, in consequence of the gradual dissipation of energy by radiation, give to the atom containing it radio-active properties similar to those conferred by the four corpuscles.”
=271. Heat of the sun and earth.= It was pointed out by Rutherford and Soddy that the maintenance of the sun’s heat for long intervals of time did not present any fundamental difficulty if a process of disintegration, such as occurs in the radio-elements, were supposed to be taking place in the sun. In a letter to Nature (July 9, 1903) W. E. Wilson showed that the presence of 3·6 grams of radium in each cubic metre of the sun’s mass was sufficient to account for the present rate of emission of energy by the sun. This calculation was based on the estimate of Curie and Laborde that 1 gram of radium emits 100 gram-calories per hour, and on the observation of Langley that each square centimetre of the sun’s surface emits 8·28 × 10⁶ gram-calories per hour. Since the average density of the sun is 1·44, the presence of radium in the sun, to the extent of 2·5 parts by weight in a million, would account for its present rate of emission of energy.
An examination of the spectrum of the sun has not so far revealed any of the radium lines. It is known, however, from spectroscopic evidence that helium is present, and this indirectly suggests the existence of radio-active matter also. It can readily be shown that the absence of penetrating rays from the sun at the surface of the earth does not imply that the radio-elements are not present in the sun. Even if the sun were composed of pure radium, it would hardly be expected that the γ rays emitted would be appreciable at the surface of the earth, since the rays would be almost completely absorbed in passing through the atmosphere, which corresponds to a thickness of 76 centimetres of mercury.
In the Appendix E of Thomson and Tait’s Natural Philosophy, Lord Kelvin has calculated the energy lost in the concentration of the sun from a condition of infinite dispersion, and concludes that it seems “on the whole probable that the sun has not illuminated the earth for 100,000,000 years and almost certain that he has not done so for 500,000,000 years. As for the future we may say, with equal certainty, that inhabitants of the earth cannot continue to enjoy the light and heat essential to their life for many million years longer, unless sources now unknown to us are prepared in the great storehouses of creation.”
The discovery that a small mass of a substance like radium can emit spontaneously an enormous quantity of heat renders it possible that this estimate of the age of the sun’s heat may be much increased. In a letter to Nature (Sept. 24, 1903) G. H. Darwin drew attention to this probability, and at the same time pointed out that, on Kelvin’s hypotheses, his estimate of the duration of the sun’s heat was probably much too high, and stated that, “The lost energy of the sun, supposed to be a homogeneous sphere of mass M and radius a, is (⅗)μM²/a where μ is the constant of gravitation. On introducing numerical values for the symbols in this formula, I find the lost energy to be 2·7 × 10⁷ M calories where M is expressed in grams. If we adopt Langley’s value of the solar constant, this heat suffices to give a supply for 12 million years. Lord Kelvin used Pouillet’s value for that constant, but if he had been able to use Langley’s, his 100 million would have been reduced to 60 million. The discrepancy between my results of 12 million and his of 60 million is explained by a conjectural augmentation of the lost energy to allow for the concentration of the solar mass towards its central parts.” Now it has been shown (section 266) that one gram of radium emits during its life an amount of heat corresponding to 1·6 × 10⁹ gram-calories. It has also been pointed out that there is every reason to suppose that a similar amount of energy is resident in the chemical atoms of the inactive elements. It is not improbable that, at the enormous temperature of the sun, the breaking up of the elements into simpler forms may be taking place at a more rapid rate than on the earth. If the energy resident in the atoms of the elements is thus available, the time during which the sun may continue to emit heat at the present rate may be at least 50 times longer than the value computed from dynamical data.
Similar considerations apply to the question of the age of the earth. A full discussion of the probable age of the earth, computed from its secular cooling from a molten mass, is given by Lord Kelvin in Appendix D of Thomson and Tait’s Natural Philosophy. He has there shown that about 100 million years after the earth was a molten mass, the gradual cooling due to radiation from its surface would account for the average temperature gradient of ¹⁄₅₀° F. per foot, observed to-day near the earth’s surface.
Some considerations will now be discussed which point to the probability that the present temperature gradient observed in the earth cannot be used as a guide to estimate the length of time that has elapsed since the earth has been at a temperature capable of supporting animal and vegetable life; for it will be shown that probably there is sufficient radio-active matter on the earth to supply as much heat to the earth as is lost by radiation from its surface. Taking the average conductivity K of the materials of the earth as ·004 (C.G.S. units) and the temperature gradient T near the surface as ·00037° C. per cm., the heat Q in gram-calories conducted to the surface of the earth per second is given by
Q = 4πR²KT,
where R is the radius of the earth.
Let X be the average amount of heat liberated per second per cubic centimetre of the earth’s volume owing to the presence of radio-active matter. If the heat Q radiated from the earth is equal to the heat supplied by the radio-active matter in the earth,
X . (⁴⁄₃)πR³ = 4πR²KT,
or 3KT X = ------ . R
Substituting the values of these constants,
X = 7 × 10⁻¹⁵ gram-calories per second = 2·2 × 10⁻⁷ gram-calories per year.
Since 1 gram of radium emits 876,000 gram-calories per year, the presence of 2·6 × 10⁻¹³ grams of radium per unit volume, or 4·6 × 10⁻¹⁴ grams per unit mass, would compensate for the heat lost from the earth by conduction.
Now it will be shown in the following chapter that radio-active matter seems to be distributed fairly uniformly through the earth and atmosphere. In addition, it has been found that all substances are radio-active to a feeble degree, although it is not yet settled whether this radio-activity may not be due mainly to the presence of a radio-element as an impurity. For example, Strutt observed that a platinum plate was about ¹⁄₃₀₀₀ as active as a crystal of uranium nitrate, or about 2 × 10⁻¹⁰ as active as radium. This corresponds to a far greater activity than is necessary to compensate for the loss of heat of the earth. A more accurate deduction, however, can be made from data of the radio-activity exhibited by matter dug out of the earth. Elster and Geitel filled a dish of volume 3·3 × 10³ c.c. with clay dug up from the garden, and placed it in a vessel of 30 litres capacity in which was placed an electroscope to determine the conductivity of the enclosed gas. After standing for several days, they found that the conductivity of the air reached a constant maximum value, corresponding to three times the normal. It will be shown later (section 284) that the normal conductivity observed in sealed vessels corresponds to the production of about 30 ions per c.c. per second. The number of ions produced per second in the vessel by the radio-active earth was thus about 2 × 10⁶. This would give a saturation current through the gas of 2·2 × 10⁻¹⁴ electromagnetic units. Now the emanation from 1 gram of radium stored in a metal cylinder gives a saturation current of about 3·2 × 10⁻⁵ electromagnetic units. Elster and Geitel considered that most of the conductivity observed in the gas was due to a radio-active emanation, which gradually diffused from the clay into the air in the vessel. The increased conductivity in the gas observed by Elster and Geitel would thus be produced by the emanation from 7 × 10⁻¹⁰ gram of radium. Taking the density of clay as 2, this corresponds to about 10⁻¹³ gram of radium per gram of clay. But it has been shown that if 4·6 × 10⁻¹⁴ gram of radium were present in each gram of earth, the heat emitted would compensate for the loss of heat of the earth by conduction and radiation. The amount of activity observed in the earth is thus about the right order of magnitude to account for the heat emission required. In the above estimate, the presence of uranium and thorium minerals in the earth has not been considered. Moreover, it is probable that the total amount of radio-activity in the clay was considerably greater than that calculated, for it is likely that other radio-active matter was present which did not give off an emanation.
If the earth is supposed to be in a state of thermal equilibrium in which the heat lost by radiation is supplied from radio-active matter, there must be an amount of radio-active matter in the earth corresponding to about 270 million tons of radium. If there were more radium than this in the earth, the temperature gradient would be greater than that observed to-day. This may appear to be a very large quantity of radium, but recent determinations (section 281) of the amount of radium emanation in the atmosphere strongly support the view that a large quantity of radium must exist in the surface soil of the earth. Eve found, on a minimum estimate, that the amount of emanation always present in the atmosphere is equivalent to the equilibrium amount derived from 100 tons of radium. There is every reason to believe that the emanation found in the atmosphere is supplied both by the diffusion of the emanation from the soil and by the action of springs. Since the emanation loses half its activity in four days, it cannot diffuse from any great depth. Assuming that the radium is uniformly distributed throughout the earth, the quantity of the radium emanation produced in a thin shell of earth about thirteen metres in depth, is sufficient to account for the amount ordinarily observed in the atmosphere.
I think we may conclude that the present rate of loss of heat of the earth might have continued unchanged for long periods of time in consequence of the supply of heat from radio-active matter in the earth. It thus seems probable that the earth may have remained for very long intervals of time at a temperature not very different from that observed to-day, and that, in consequence, the time during which the earth has been at a temperature capable of supporting the presence of animal and vegetable life may be very much longer than the estimate made by Lord Kelvin from other data.
=272. Evolution of matter.= Although the hypothesis that all matter is composed of some elementary unit of matter or protyle has been advanced as a speculation at various times by many prominent physicists and chemists, the first definite experimental evidence showing that the chemical atom was not the smallest unit of matter was obtained in 1897 by J. J. Thomson in his classic research on the nature of the cathode rays produced by an electric discharge in a vacuum tube. We have seen that Sir William Crookes, who was the first to demonstrate the remarkable properties of these rays, had suggested that they consisted of streams of projected charged matter and represented—as he termed it—a new or “fourth state of matter.”
J. J. Thomson showed by two distinct methods (section 50), that the cathode rays consisted of a stream of negatively charged particles projected with great velocity. The particles behaved as if their mass was only about ¹⁄₁₀₀₀ of the mass of the atom of hydrogen, which is the lightest atom known. These corpuscles, as they were termed by Thomson, were found at a later date to be produced from a glowing carbon filament and from a zinc plate exposed to the action of ultra-violet light. They acted as isolated units of negative electricity, and, as we have seen, may be identified with the electrons studied mathematically by Larmor and Lorentz. Not only were these electrons produced by the action of light, heat, and the electric discharge, but similar bodies were also found to be emitted spontaneously from the radio-elements with a velocity far greater than that observed for the electrons in a vacuum tube.
The electrons produced in these various ways were all found to carry a negative charge, and to be apparently identical; for the ratio e/m of the charge of the electron to its mass was in all cases the same within the limits of experimental error. Since electrons, produced from different kinds of matter and under different conditions, were in all cases identical, it seemed probable that they were a constituent part of all matter. J. J. Thomson suggested that the atom is built up of a number of these negatively charged electrons combined in some way with corresponding positively charged bodies.
On this view the atoms of the chemical elements differ from one another only in the number and arrangement of the component electrons.
The removal of an electron from the atom in the case of ionization does not appear to affect permanently the stability of the system, for no evidence has so far been obtained to show that the passage of an intense electric discharge through a gas results in a permanent alteration of the structure of the atom. On the other hand, in the case of the radio-active bodies, a positively charged particle of mass about twice that of the hydrogen atom escapes from the heavy radio-atom. This loss appears to result at once in a permanent alteration of the atom, and causes a marked change in its physical and chemical properties. In addition there is no evidence that the process is reversible.
The expulsion of a β particle with great velocity from an atom of radio-active matter also results in a transformation of the atom. For example radium E emits a β particle, and, in consequence, gives rise to a distinct substance radium F (polonium). A case of this kind, where the expulsion of a β particle with great velocity causes a complete rearrangement of the parts of an atom, is probably quite distinct from the process which occurs during ionization, where a slow speed electron escapes from the atom without apparently affecting the stability of the atom left behind.
The only direct experimental evidence of the transformation of matter has been derived from a study of the radio-active bodies. If the disintegration theory, advanced to account for the phenomena of radio-activity, is correct in the main essentials, then the radio-elements are undergoing a spontaneous and continuous process of transformation into other and different kinds of matter. The rate of transformation is slow in uranium and thorium, but is fairly rapid in radium. It has been shown that the fraction of a mass of radium which is transformed per year is about ¹⁄₂₀₀₀ of the total amount present. In the case of uranium and thorium probably a million years would be required to produce a similar amount of change. Thus the process of transformation in uranium and thorium is far too slow to be detected within a reasonable time by the use of the balance or spectroscope, but the radiations which accompany the transformation can easily be detected. Although the process of change is slow it is continuous, and in the course of ages the uranium and thorium present in the earth must be transformed into other types of matter.
Those who have considered the possibility of atoms undergoing a process of transformation have generally thought that the matter as a whole would undergo a progressive change, with a gradual alteration of physical and chemical properties of the whole mass of substance. On the theory of disintegration this is not the case. Only a minute fraction of the matter present breaks up in unit time, and in each of the successive stages through which the disintegrated atoms pass, there is in most cases a marked alteration in the chemical and physical properties of the matter. The transformation of the radio-elements is thus a transformation of a part per saltum, and not a progressive change of the whole. At any time after the process of transformation has been in progress there will thus remain a part of the matter which is unchanged, and, mixed with it, the products which have resulted from the transformation of the remainder.
The question naturally arises whether the process of degradation of matter is confined to the radio-elements or is a universal property of matter. It will be shown in chapter XIV that all matter, so far examined, exhibits the property of radio-activity to a slight degree. It is very difficult, however, to make certain that the observed radio-activity is not due to the presence in the matter of a slight trace of a radio-element. If ordinary matter is radio-active, it is certain that its activity is much less than that of uranium, and consequently that its rate of transformation must be excessively slow. There is, however, another possibility to be considered. The changes occurring in the radio-elements would probably never have been detected if the change had not been accompanied by the expulsion of charged particles with great velocity. It does not seem unlikely that an atom may undergo disintegration without projecting a part of its system with sufficient velocity to ionize the gas. In fact, we have seen that, even in the radio-elements, several of the series of changes in both thorium, radium, and actinium are unaccompanied by ionizing rays. The experimental results given in Appendix A strongly support this point of view. It may thus be possible that all matter is undergoing a slow process of transformation, which has so far only been detected in the radio-elements on account of the expulsion of charged particles with great velocity during the change. This process of degradation of matter continuing for ages must reduce the constituents of the earth to the simpler and more stable forms of matter.
The idea that helium is a transformation product of radium suggests the probability that helium is one of the more elementary substances of which the heavier atoms are composed. Sir Norman Lockyer, in his interesting book on “Inorganic Evolution,” has pointed out that the spectra of helium and of hydrogen predominate in the hottest stars. In the cooler stars the more complex types of matter appear. Sir Norman Lockyer has based his theory of evolution of matter on evidence of a spectroscopic examination of the stars, and considers that temperature is the main factor in breaking up matter into its simpler forms. The transformation of matter occurring in the radio-elements is on the other hand spontaneous, and independent of temperature over the range examined.
Footnote 333:
Perrin, Revue Scientifique, April 13, 1901.
Footnote 334:
Becquerel, C. R. 133, p. 979, 1901.
Footnote 335:
Rutherford and McClung, Phil. Trans. A, p. 25, 1901.
Footnote 336:
Rutherford, Phil. Mag. Jan. and Feb. 1900.
Footnote 337:
P. Curie, C. R. 136, p. 223, 1903.
Footnote 338:
Rutherford, Phil. Mag. April, 1903.
Footnote 339:
M. and Mme Curie, C. R. 134, p. 85, 1902.
Footnote 340:
Rutherford and Soddy, Trans. Chem. Soc. 81, pp. 321, 837, 1902. Phil. Mag. Sept. and Nov. 1902.
Footnote 341:
Rutherford and Soddy, Phil. Mag. April, 1903.
Footnote 342:
Rutherford and Soddy, Phil. Mag. May, 1903.
Footnote 343:
Rutherford, Phys. Zeit. 4, p. 235, 1902. Phil. Mag. Feb. 1903.
Footnote 344:
Rutherford, Phil. Mag. May, 1903.
Footnote 345:
Curie and Laborde, C. R. 136, p. 673, 1903.
Footnote 346:
J. J. Thomson, Nature, p. 601, 1903.
Footnote 347:
Crookes, C. R. 128, p. 176, 1899.
Footnote 348:
F. Re, C. R. p. 136, p. 1393, 1903.
Footnote 349:
Richarz and Schenck, Berl. Ber. p. 1102, 1903. Schenck, Berl. Ber. p. 37, 1904.
Footnote 350:
Armstrong and Lowry, Proc. Roy. Soc. 1903. Chem. News, 88, p. 89, 1903.
Footnote 351:
Rutherford and Soddy, Phil. Mag. May, 1903.
Footnote 352:
Boltwood, Nature, May 25, p. 80, 1904. Phil. Mag. April, 1905.
Footnote 353:
McCoy, Ber. d. D. Chem. Ges. No. 11, p. 2641, 1904.
Footnote 354:
Strutt, Nature, March 17 and July 7, 1904. Proc. Roy. Soc. March 2, 1905.
Footnote 355:
Strutt, Proc. Roy. Soc. March 2, 1905.
Footnote 356:
Soddy, Nature, May 12, 1904; Jan. 19, 1905.
Footnote 357:
Whetham, Nature, May 5, 1904; Jan. 26, 1905.
Footnote 358:
Danne, C. R. Jan. 23, 1905.
Footnote 359:
J. J. Thomson, Nature, April 30, p. 601, 1903.
Footnote 360:
Voller, Phys. Zeit. 5, No. 24, p. 781, 1904.
Footnote 361:
Ramsay and Cooke, Nature, Aug. 11, 1904.
Footnote 362:
Eve, Nature, March 16, 1905.
Footnote 363:
J. J. Thomson, International Electrical Congress, St Louis, Sept. 1904.
Footnote 364:
Rutherford and Soddy, Phil. Mag. p. 582, 1902; pp. 453 and 579, 1903.
Footnote 365:
Ramsay and Soddy, Nature, July 16, p. 246, 1903. Proc. Roy. Soc. 72, p. 204, 1903; 73, p. 346, 1904.
Footnote 366:
Curie and Dewar, C. R. 138, p. 190, 1904. Chem. News, 89, p. 85, 1904.
Footnote 367:
Himstedt and Meyer, Ann. d. Phys. 15, p. 184, 1904.
Footnote 368:
Strutt, Proc. Roy. Soc. March 2, 1905.
Footnote 369:
Boltwood, Phil. Mag. April, 1905.
Footnote 370:
Moss, Trans. Roy. Soc. Dublin, 1904.
Footnote 371:
Travers, Nature, p. 248, Jan. 12, 1905.
Footnote 372:
Jaquerod, C. R. p. 789, 1904.
Footnote 373:
Ramsay and Travers, Zeitsch. Physik. Chem. 25, p. 568, 1898.
Footnote 374:
Ramsay, Nature, April 7, 1904.
Footnote 375:
Lodge, Nature, June 11, p. 129, 1903.
Footnote 376:
Larmor, Aether and Matter, p. 233.
Footnote 377:
J. J. Thomson, Phil. Mag. p. 681, Dec. 1903.
Footnote 378:
Lord Kelvin, Phil. Mag. Oct. 1904.
Footnote 379:
Thomson, Phil. Mag. March, 1904.
Footnote 380:
Rutherford and Soddy, Phil. Mag. May, 1903.
Footnote 381:
See Strutt and Joly, Nature, Oct. 15, 1903.
Footnote 382:
Strutt, Phil. Mag. June, 1903.
Footnote 383:
Elster and Geitel, Phys. Zeit. 4, No. 19, p. 522, 1903. Chem. News, July 17, p. 30, 1903.
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