Popular Science Monthly/Volume 66/November 1904/The Present Problems of Inorganic Chemistry
| THE PRESENT PROBLEMS OF INORGANIC CHEMISTRY.[1] |
By Sir WILLIAM RAMSAY, K.C.B., F.R.S.
TO discuss the 'present problems of inorganic chemistry' is by no means an easy task. The expression might be taken to mean an account of what is being actually done at present by those engaged in inorganic research; or it might be taken to relate to what needs doing—to the direction in which research is required. To summarize what is being done in an intelligible manner in the time at my disposal would be an almost impossible task; hence I will choose the latter interpretation of the title of my address. Now, a considerable experience in attempting to unveil the secrets of nature has convinced me that a deliberate effort to discover some new law or fact seldom succeeds. The investigator generally begins unmethodically, by random and chance experiments; or perhaps he is guided by some indication which has struck his attention during some previous research; and he is often the plaything of circumstances in his choice. Experience leads him to choose problems which most readily admit of solution, or which appear likely to lead to the most interesting results. If I may be excused the egotism of referring to my own work, I may illustrate what I mean by relating the following curious coincidence: After Lord Rayleigh had announced his discovery that 'atmospheric nitrogen' was denser than 'chemical nitrogen' I referred to Cavendish's celebrated paper on the combination of the nitrogen and the oxygen the air by means of electric sparks. Fortified by what I read, and by the knowledge gained during the performance of lecture experiments that red-hot magnesium is a good and fairly rapid absorbent of nitrogen, it was not long before a considerable quantity of nearly pure argon had been separated from atmospheric nitrogen. Now it happened that I possess two copies of Cavendish's works; and some months afterwards I consulted the other copy and found penciled on the margin the words 'look into this.' I remembered the circumstance which led to the annotation. About ten years before, one of my students had investigated the direct combination of nitrogen and hydrogen, and I had read Cavendish's memoir on that occasion. I mention this fact to show that for some reason which I forget, a line of work was not followed up, which would have been attended by most interesting results; one does not always follow the clue which yields results of the greatest interest. I regard it therefore as an impossible task to indicate the lines on which research should be carried out. All that I can do is to call attention to certain problems awaiting solution; but their relative importance must necessarily be a matter of personal bias, and others might with perhaps greater right suggest wholly different problems.
The fundamental task of inorganic chemistry is still connected with the classification of elements and compounds. The investigation of the classification of carbon compounds forms the field of organic chemistry; while general or physical chemistry deals with the laws of reaction, and the influence of various forms of energy in furthering or hindering chemical change. And classification centers at present in the periodic arrangement of the elements, according to the order of their atomic weights. Whatever changes in our views may be concealed in the lap of the future, this great generalization, due to Newlands, Lothar Meyer and Mendelejev, will always retain a place, perhaps the prominent place, in chemical science.
Now it is certain that no attempt to reduce the irregular regularity of the atomic weights to a mathematical expression has succeeded; and it is, in my opinion, very unlikely that any such expression, of not insuperable complexity, and having a basis of physical meaning, will ever be found. I have already, in an address to the German Association at Cassel, given an outline of the grand problem which awaits solution. It can be shortly stated then: While the factors of kinetic and of gravitational energy, velocity and momentum, on the one hand, and force and distance, on the other, are simply related to each other, the capacity factors of other forms of energy—surface, in the case of surface-energy; volume, in the case of volume-energy; entropy for heat; electric capacity when electric charges are being conveyed by means of ions; atomic weight, when chemical energy is being gained or lost—all these are simply connected with the fundamental chemical capacity, atomic weight or mass. The periodic arrangement is an attempt to bring the two sets of capacity factors into a simple relation to each other; and while the attempt is in so far a success, inasmuch as it is evident that some law is indicated, the divergences are such as to show that finality has not been attained. The central problem in inorganic chemistry is to answer the question—why this incomplete concordance? Having stated the general question, it may conduce to clearness if some details are given.
1. The variation of molecular surface energy with temperature is such that the surface-energy, for equal numbers of molecules distributed over a surface, is equal for equal intervals of temperature below the temperature at which surface-energy is zero—that is, the critical point. This gives a means of determining the molecular weights of liquids, and we assume that the molecular weight of a compound is accurately the sum of the atomic weights of the constituent elements.
2. The volume-energy of gases is equal at equal temperature from that at which volume-energy is zero—i. e., absolute zero. And it follows that those volumes of gases which possess equal volume-energy contain equal numbers of molecules—again, a close connection with atomic weights.
3. The specific heats of elements are approximately inversely proportional to their atomic weights; and of compounds to the quotient of their molecular weights divided by the number of atoms in the molecule. Specific heat and entropy are closely related; hence one of the factors of thermal energy is proportional (nearly) to the reciprocal of the atomic weights.
4. The ion carries in its migration through a solution one or more electrons. Now, the ion is an atom carrying one or more charges—one for each equivalent. Here we have the capacity for electric charge proportional to the equivalent.
5. The factors of chemical energy are atomic weight and chemical potential; and as the former is identical numerically, or after multiplication by a simple factor with equivalent, electric potential is proportional to chemical potential.
We see therefore that surface, volume, thermal, electrical, and, no doubt, other forms of energy have as capacity factors magnitudes, either identical with, or closely related to, units of chemical capacity; while kinetic and linear energy are not so related, except through the periodic arrangement of the elements.
It appears therefore to be a fundamental problem for the chemist to ascertain, first, accurate atomic weights, and, second, to investigate some anomalies which still present difficulties. In America, you have excellent workers in the former branch. Mallet, Morley, Richards and many others have devoted their time and skill to perhaps the best work of this kind which has been done; and F. W. Clarke has collated all results and afforded incalculable help to all who work at or are interested in the subject. Valuable criticisms, too, have been made by Hinrichs; but it must be confessed that in spite of these, which are perhaps the best determinations which have been made, the problem becomes more, and not less formidable.
There are lines of work, however, which suggest themselves as possibly likely to throw light on the question. First, there is a striking anomaly in the atomic weight of nitrogen, determined by analysis and determined by density. Stas obtained the number 14.04 , and Richards has recently confirmed his results; while Rayleigh and Leduc consistently obtained densities which, even when corrected so as to equalize the numbers of molecules in equal volumes, give the lower figure 14.002. The difference is 1 in 350; far beyond any possible experimental error. Recently, an attempt to combine the two methods has led to a mean number; but that result can hardly be taken as final. What is the reason of the discrepancy? Its discovery will surely advance knowledge materially. I would suggest the preparation of pure compounds of nitrogen, such as salts of hydrazine, methylanine, etc., and their careful analysis; and also the accurate determination of the density and analysis of such gaseous compounds of nitrogen as nitric oxide and peroxide. I have just heard from my former student, W. E. W. Gray, that he has recovered Stas's number by combining 2NO with O2; while the density of NO leads to the lower value for the atomic weight of nitrogen.
The question of the atomic weight of tellurium appears to be settled, at least so far as its position with regard to the generally accepted atomic weight of iodine is concerned; recent determinations give the figures 127.5 (Gutbier), 127.6 (Pellini), and 127.9 (Köthner). But is that of iodine as accurately known? It would appear advisable to revise the determination of Stas, preparing the iodine preferably from an organic compound, such as iodoform, which can be produced in a high state of purity. The heteromorphism of selenates and tellurates, too, has recently been demonstrated; and it may be questioned whether these elements should both belong to the same group.
The rare earths still remain a puzzle. Their number is increasing yearly, and their claim to individuality admits of less and less dispute. What is to be done with them? Are they to be grouped by themselves as Brauner and Steele propose? If so, how is their connection with the other elements to be explained? Recent experiments in my laboratory have convinced me that in the case of thorium, at least, ordinary tests of purity such as fine crystals, constant subliming point, etc., do not always indicate homogeneity; or else that we are sadly in want of some analytical method of sufficient accuracy. The change of thorium into thorium X is perhaps hardly an explanation of the divergencies; yet it must be considered; but of this, more anon.
To turn next to another problem closely related to the orderly arrangement of the elements—that of valency—but little progress can be chronicled. The suggestions which have been made are speculative, rather than based on experiment. The existence of many peroxidized substances, such as percarbonates, perborates, persulphates and of crystalline compounds of salts with hydrogen peroxide, makes it difficult to draw any indisputable conclusions as regards valency from a consideration of oxygen compounds. Moissan's brilliant work on fluorides, however, has shown that SF6 is capable of stable existence, and this forms a strong argument in support of the hexad character of sulphur. The tetravalency of oxygen, under befitting conditions, too, is being acknowledged, and this may be reconciled with the existence of water of crystallization, as well as of the per-salts already mentioned. The adherence of ammonia to many chlorides, nitrates, etc., points to the connecting link being ascribable to the pentavalency of nitrogen; and it might be worth while investigating similar compounds with phosphoretted and arsenicoretted hydrogen, especially at low temperatures.
The progress of chemical discovery, indeed, is closely connected with the invention of new methods of research, or the submitting of matter to new conditions. While Moissan led the way by elaborating the electric furnace, and thus obtained a potent agent in temperatures formerly unattainable, Spring has tried the effect of enormous pressure, and has recently found chemical action between cuprous oxide and sulphur at ordinary temperature, provided the pressure be raised to 8,000 atmospheres. Increase of pressure appears to lower the temperature of reaction. It has been known for long that explosions will not propagate in rarefied gases, and that they become more violent when the reacting gases are compressed: but we are met with difficulties, such as the non-combination of hydrogen and nitrogen, even at high temperature and great pressure; yet it is possible to measure the electromotive force (0.59 volt) in a couple consisting of gaseous nitrogen and gaseous hydrogen, the electrolyte being a solution of ammonium nitrate saturated with ammonia. Chemical action between dissolved hydrogen and nitrogen undoubtedly occurs; but it is not continuous. Again we may ask, Why? The heat evolution should be great; the gain of entropy should also be high were direct combination to occur. Why does it not occur to any measurable extent? Is it because for the initial stages of any chemical reaction, the reacting molecules must be already dissociated, and those of nitrogen are not? Is that in any way connected with the abnormally low density of gaseous nitrogen? Or is it that, in order that combination shall occur, the atoms must fit each other; and that in order that nitrogen and hydrogen atoms may fit, they must be greatly distorted? But these are speculative questions, and it is not obvious how experiments can be devised to answer them.
Many compounds are stable at low temperatures which dissociate when temperature is raised. Experiments are being made, now that liquid air is to be purchased or cheaply 'made, on the combinations of substances which are indifferent to each other at ordinary temperatures. Yet the research must be a restricted one, for most substances are solid at — 185°, and refuse to act on each other. It is probable, however, that at low temperatures compounds could be formed in which one of the elements would possess a greater valency than that usually ascribed to it; and also that double compounds of greater complexity would prove stable. Valency, indeed, appears to be in many cases a function of temperature; exothermic compounds, as is well known, are less stable, the higher the temperature. The sudden cooling of compounds produced at a high temperature may possibly result in forms being preserved which are unstable at ordinary temperatures. Experiments have been made in the hope of obtaining compounds of argon and helium by exposing various elements to the influence of sparks from a powerful induction coil, keeping the walls of the containing-vessel at the temperature of liquid air, in the hope that any endothermic compound which might be formed would be rapidly cooled, and would survive the interval of temperature at which decomposition would take place naturally. But these experiments have so far yielded only negative results. There is some indication, however, that such compounds are stable at 1,500°. It might be hoped that a study of the behavior of the non-valent elements would have led to some conception of the nature of valency; but so far, no results bearing on the question have transpired. The condition of helium in the minerals from which it is obtainable by heat is not explained; and experiments in this direction have not furnished any positive information. It is always doubtful whether it is advisable to publish the results of negative experiments; for it is always possible that some more skilled or more fortunate investigator may succeed, where one has failed. But it may be chronicled that attempts to cause combination between the inactive gases and lithium, potassium, rubidium, and caesium have yielded no positive results; nor do they appear to react with fluorine. Yet conditions of experiment play a leading part in causing combination, as has been well shown by Moissan with the hydrides of the alkali-metals, and by Guntz, with those of the metals of the alkaline earths. The proof that sodium hydride possesses the formula NaH, instead of the formerly accepted one, removes one difficulty in the problem of valency; and SrH2 falls into its natural position among hydrides.
A fertile field of inorganic research lies in the investigation of structure. While the structure of organic compounds has been elucidated almost completely, that of inorganic compounds is practically undeveloped. Yet efforts have been made in this direction which appear to point a way. The nature of the silicates has been the subject of research for many years by F. W. Clarke; and the way has been opened. Much may be done by treating silicates with appropriate solvents, acid or alkaline, which differentiate between uncombined and combined silica, and which in some cases, by replacement of one metal by another, gives a clue to constitution. The complexity of the molecules of inorganic compounds, which are usually solid, forms another bar to investigation. It is clear that sulphuric acid, to choose a common instance, possesses a very complicated molecule; and the fused nitrates of sodium and potassium are not correctly represented by the simple formula? NaNO3 and KNO3. Any theory of the structure of their derivatives must take such facts into consideration; but we appear to be getting nearer the elucidation of the molecular weights of solids. Again, the complexity of solutions of the most common salts is maintained by many investigators; for example, a solution of cobalt chloride, while it undoubtedly contains among other constituents simple molecules of CoCl2, also consists of ions of a complex character, such as (CoCl4)″. And what holds for cobalt chloride also undoubtedly holds for many similar compounds.
In determining the constitution of the compounds of carbon, stereo-chemistry has played a great part. The ordinary structural formulæ are now universally acknowledged to be only pictorial, if, indeed, that word is legitimate; perhaps it would be better to say that they are distorted attempts at pictures, the drawing of which is entirely free from all rules of perspective. But these formulæ may in almost every case be made nearly true pictures of the configuration of the molecules. The benzine formula, to choose an instance which is by no means the simplest, has been shown by Collie to be imitated by a model which represents in an unstrained manner the behavior of that body on treatment with reagents. But in the domain of inorganic chemistry, little progress has been made. Some ingenious ideas of the geologist Sollas on this problem have hardly received the attention which they deserve; perhaps they may have been regarded as too speculative. On the other hand, Le Bel's and Pope's proof of the stereo-isomerism of certain compounds of nitrogen; Pope's demonstration of the tetrahedral structure of the alkyl derivatives of tin; and Smiles's syntheses of stereo-isomeric sulphur compounds give us the hope that further investigation will lead to the classification of many other elements from this point of view. Indeed, the field is almost virgin soil; but it is well worth while cultivating. There is no doubt that the investigation of other organo-metallic compounds will result in the discovery of stereo-isomerides; yet the methods of investigation capable of separating such constituents have in most cases still to be discovered.
The number of chemical isomerides among inorganic compounds is a restricted one. Werner has done much to elucidate this subject in the case of complex ammonia derivatives of metals and their salts; but there appears to be little doubt that if looked for, the same or similar phenomena would be discoverable in compounds with much simpler formulas. The two forms of So3, sulphuric anhydride, are an instance in point. No doubt formation under different conditions of temperature and pressure might result in the greater stability of some forms which under our ordinary conditions are changeable and unstable. The fact that under higher pressures than are generally at our disposal different forms of ice have been proved to exist, and the application of the phase-rule to such cases, will greatly enlarge our knowledge of molecular isomerism.
The phenomena of catalysis have been extensively studied of recent years, and have obviously an important bearing on such problems. A catalytic agent is one which accelerates or retards the velocity of reaction. Without inquiring into the mechanism of catalysis, its existence may be made to influence the rate of chemical change, and to render stable bodies which under ordinary conditions are unstable. For if it is possible to accelerate a chemical change in such a way that the usually slow and possibly unrecognizable rate of isomeric change may be made apparent and measurable, a substance the existence of which could not be recognized under ordinary circumstances, owing to its infinitesimal amount, may be induced to exist in weighable quantity, if the velocity of its formation from an isomeride can be greatly accelerated by the presence of an appropriate catalytic agent. I am not aware that attempts have been made in this direction. The discovery of catalytic agents is, as a rule, the result of accident. I do not think that any guide exists which would enable us to predict that any particular substance would cause an acceleration or a retardation of any particular reaction. But catalytic agents are generally those which themselves, by their power of combining with or parting with oxygen, or some other element, cause the transfer of that element to other compounds to take place with increased or diminished velocity. It is possible, therefore, to cause ordinary reactions to take place in presence of a third body, choosing the third body with a view to its catalytic action, and to examine carefully the products of the main reaction as regards their nature and their quantity. Attempts have been made in this direction with marked success; the rate of change of hydrogen dioxide, for example, has been fairly well studied. But what has been done for that compound may be extended indefinitely to others, and doubtless with analogous results. Indications of the existence of as yet undiscovered compounds may be derived from a study of physical, and particularly of electrical, changes. There appears to be sufficient evidence of an oxide of hydrogen containing more oxygen than hydrogen dioxide, from a study of the electromotive force of a cell containing hydrogen dioxide; yet the higher oxide still awaits discovery.
The interpretation of chemical change in the light of the ionic theory may now be taken as an integral part of inorganic chemistry. The ordinary reactions of qualitative and quantitative analysis are now almost universally ascribed to the ions, not to the molecules. And the study of the properties of most ions falls into the province of the inorganic chemist. To take a familiar example: The precipitation of hydroxides by means of ammonia-solution has long led to the hypothesis that the solution contained ammonium hydroxide; and, indeed, the teaching of the text-books and the labels on the bottles supported this view. But we know now that a solution of ammonia in water is a complex mixture of liquid ammonia and liquid water; of ammonium hydroxide, NH4OH; and of ions of ammonium (NH4)′, and hydroxyl (OH)′. Its reactions, therefore, are those of such a complex mixture. If brought into contact with a solution of some substance which will withdraw the hydroxyl ions, converting them into water, or into some non-ionized substance, they are replaced at the expense of the molecules of non-ionized ammonium hydroxide; and these, when diminished in amount, draw on the store of molecules of ammonia and water, which combine, so as to maintain equilibrium, Now the investigation of such changes must belong to the domain of inorganic chemistry. It is true that the methods of investigation are borrowed from the physical chemist; but the products lie in the province of the inorganic chemist. Indeed, the different departments of chemistry are so interlaced that it is impossible to pursue investigations in any one branch without borrowing methods from the others; and the inorganic chemist must be familiar with all chemistry, if he is to make notable progress in his own branch of the subject. And if the substances and processes investigated by the inorganic chemist are destined to become commercially important, it is impossible to place the manufacture on a sound commercial basis without ample knowledge of physical methods, and their application to the most economical methods of accelerating certain reactions and retarding others, so as to obtain the largest yield of the required product at the smallest cost of time, labor and money.
I have endeavored to sketch some of the aspects of inorganic chemistry with a view to suggesting problems for solution, or at least the directions in which such problems are to be sought. But the developments of recent years have been so astonishing and so unexpected, that I should fail in my duty were I not to allude to the phenomena of radioactivity, and their bearing on the subject of my address. It is difficult to gauge the relative importance of investigations in this field; but I may be pardoned if I give a short account of what has already been done, and point out lines of investigation which appear to me likely to yield useful results.
The wonderful discovery of radium by Madame Curie, the preparation of practically pure compounds of it, and the determination of its atomic weight are familiar to all of you. Her discovery of polonium, and Debierne's of actinium have also attracted much attention. The recognition of the radioactivity of uranium by Becquerel, which gave the first impulse to these discoveries, and of that of thorium by Schmidt, is also well known.
These substances, however, presented at first more interest for the physicist than the chemist, on account of the extraordinary power which they all possess of emitting 'rays.' At first, these rays were supposed to constitute ethereal vibrations; but all the phenomena were not explicable on that supposition. Schmidt first, and Rutherford and Soddy later, found that certain so-called 'rays' really consist of gases; and that while thorium emits one kind, radium emits another; and no doubt Debierne's actinium emits a third. The name 'emanations' was applied by Rutherford to such radioactive bodies; he and Soddy found that those of radium and thorium could be condensed and frozen by exposure to the temperature of liquid air, and that they were not destroyed or altered in any way by treatment with agents which are able to separate all known gases from those of the argon group, namely, red-hot magnesium-lime, and it was later found that sparking with oxygen in presence of caustic potash did not affect the gaseous emanation from radium. The conclusion therefore followed that in all probability these bodies are gases of the argon group, the atomic weight of which, and consequently the density, is very high; indeed, several observers, by means of experiments on the rate of diffusion of the gas from radium, believe it to have a density of approximately 100, referred to the hydrogen standard. This conclusion has been confirmed by the mapping of the spectrum of the radium emanation, which is similar in general character to the spectra of the inactive gases, consisting of a number of well-defined, clearly cut brilliant lines, standing out from a black background. The volume of the gas produced spontaneously from a given weight of radium bromide in a given time has been measured; and it was incidentally shown that this gas obeys Boyle's law of pressures. The amount of gas thus collected and measured, however, was very minute; the total quantity was about the forty-thousandth of a cubic centimeter.
Having noticed that those minerals which consist of compounds of uranium and thorium contain helium, Rutherford and Soddy made the suggestion that it might not be impossible that helium is the product of the spontaneous change of the emanation; and Soddy and I were able to show that this is actually the case. For, first, when a quantity of a radium salt which has been prepared for some time is dissolved in water, the occluded helium is expelled, and can be recognized by means of its spectrum; further, the fresh emanation shows no helium spectrum, but after a few days the spectrum of helium begins to appear, proving that a spontaneous change is in progress; and last, as the emanation disappears its volume decreases to zero; and on heating the capillary glass tube which contained it, helium is driven out from the glass walls, into which its molecules had been imbedded in volume equal to three and a half times that of the emanation. The α-rays, as foreshadowed by Rutherford and Soddy, consist of helium particles.
All these facts substantiate the theory, devised by Rutherford and Soddy, that the radium atom is capable of disintegration, one of the products being a gas, which itself undergoes further disintegration, forming helium as one of its products. Up till now, the sheet anchor of the chemists has been the atom. But the atom itself appears to be complex, and to be capable of decomposition. It is true that only in the case of a very few elements, and these of high atomic weight, has this been proved. But even radium, the element which has by far the most rapid rate of disintegration, has a comparatively long life; the period of half-change of any given mass of radium is approximately 1,100 years. The rate of change of the other elements is incomparably slower. This change, too, at least in the case of radium, and its emanation, and presumably also in the case of other elements, is attended with an enormous loss of energy. It is easy to calculate from heat measurements (and independent and concordant measurements have been made) that one pound of emanation is capable of parting with as much energy as several hundred tons of nitroglycerine. The order of the quantity of energy evolved during the disintegration of the atom is as astonishing as the nature of the change. But the nature of the change is parallel to what would take place if an extremely complicated hydrocarbon were to disintegrate; its disruption into simpler paraffins and defines would also be attended with loss of energy. We may therefore take it, I think, that the disintegration hypothesis of Rutherford and Soddy is the only one which will meet the case.
If radium is continually disappearing, and would totally disappear in a very few thousand years, it follows that it must be reproduced from other substances, at an equal rate. The most evident conjecture, that it is formed from uranium, has not been substantiated. Soddy has shown that salts of uranium, freed from radium, and left for a year, do not contain one ten-thousandth part of the radium that one would expect to be formed in the time. It is evident therefore that radium must owe its existence to the presence of some other substances, but what they are is still unascertained.
During the investigation of Rutherford and Soddy of the thorium emanation, a most interesting fact was observed, namely, that precipitation of the thorium as hydroxide by ammonia left unprecipitated a substance, which they termed thorium-X, and which was itself highly radio-active. Its radio-active life, however, was a short one; and as it decayed, it was reproduced from its parent thorium at an equal rate. Here is a case analogous to what was sought for with radium and uranium; but evidently uranium is not the only parent of radium; the operation is not one of parthenogenesis. Similar facts have been elicited for uranium by Crookes.
The α-rays, caused by the disintegration of radium and of its emanation, are accompanied by rays of quite a different character; they are the β-rays, identical with electrons, the mass of which has been measured by J. J. Thomson and others. These particles are projected with enormous velocity, and are capable of penetrating glass and metal screens. The power of penetration appears to be proportional to the amount of matter in the screen, estimated by its density. These electrons are not matter; but, as I shall relate, they are capable of causing profound changes in matter.
For the past year, a solution of radium bromide has been kept in three glass bulbs each connected to a Topler pump by means of capillary tubing. To ensure these bulbs against accident, each was surrounded by a small beaker; it happened that one of these beakers consisted mainly of potash glass; the other two were of soda glass. The potash-glass beaker became brown, while the two soda-glass beakers became purple. I think there is every probability that the colors are due to liberation of the metals potassium and sodium in the glass. They are contained in that very viscous liquid, glass, in the colorless ionic state; but these ions are discharged by the β-rays, or negative electrons, and each metal imparts its own peculiar color to the glass, as has been shown by Maxwell Garnett. This phenomenon, however interesting, is not the one to which I desire to draw special attention. It must be remembered that the beakers have been exposed only to β-rays; α-rays have never been in contact with them; they have never been bombarded by what is usually called matter, except by the molecules of the surrounding air. Now these colored beakers are radioactive, and the radioactive film dissolves in water. After careful washing, the glass was no longer radioactive. The solution contains an emanation, for on bubbling air through it, and cooling the issuing air with liquid air, part of the radioactive matter was retained in the cooled tube. This substance can be carried into an electroscope by a current of air, after the liquid air has been withdrawn, and as long as the air-current passes, the electroscope is discharged; the period of decay of this emanation, however, is very rapid, and on ceasing the current of air, the leaves of the electroscope cease to be discharged. In having such a short period of existence, this emanation resembles the one from actinium.
Owing to the recess, only a commencement has been made with the investigation of the residue left on evaporation of the aqueous solution. On evaporation, the residue is strongly active. Some mercurous nitrate was then added to the dissolved residue, and it was treated with hydrochloric acid in excess, to precipitate mercurous chloride. The greater part of the active matter was thrown down with the mercurous chloride, hence it appears to form an insoluble chloride. The mercurous chloride retained its activity unchanged in amount for ten days. The filtrate from the mercurous chloride, on evaporation, turned out to be active; and on precipitating mercuric sulphide in it, the sulphide precipitate was also active; but its activity decayed in one day. The filtrate from the mercuric sulphide gave inactive precipitatates with ferric salts and ammonia, with zinc salts and ammonium sulphide, with calcium salts and ammonium carbonate; and on final evaporation, the residue was not radioactive. Hence the active matter forms an insoluble chloride and sulphide. The precipitated mercurous chloride and mercuric sulphide were dissolved in aqua regia, and the solution was evaporated. The residue was dissolved in water, and left the dish inactive. But the solution gave an insoluble sulphate, when barium chloride and sulphuric acid were added to it, hence the radioactive element forms an insoluble sulphate, as well as an insoluble chloride and sulphide.
This is a sample of the experiments which have been made. It may be remarked that the above results were obtained from a mixture of the potash and soda glass; somewhat different results were obtained from the potash glass alone. These changes appear to be due to the conversion of one or more of the constituents of the glass into other bodies. Needless to say, neither of the samples of glass contained lead.
I have mentioned these experiments in detail, because I think they suggest wholly new lines of investigation. It would appear that if energy can be poured into a definite chemical matter, such as glass, it undergoes some change, and gives rise to bodies capable of being tested for; I imagine that radio-active forms of matter are produced, either identical with or allied to, those at present known. And just as radium and other radio-active elements suffer degradation spontaneously, evolving energy, so I venture to think that if energy be concentrated in the molecules of ordinary forms of matter, a sort of polymerization is the result, and radio-active elements, probably elements with high atomic weight, and themselves unstable, are formed. Of course further research may greatly modify these views; but some guide is necessary, and Mr. Ternent Cook, who has helped me in these experiments, and I suggest this hypothesis (in the words of Dr. Johnstone Stoney, a hypothesis is 'a supposition which we hope ma} r be useful') to serve as a guide for future endeavor.
In the light of such facts, speculation on the periodic arrangement of the elements is surely premature. It is open to any one to make suggestions; they are self-evident. Most of you will agree with the saying 'it is easy to prophesy after the event.' I prefer to wait until prophecy becomes easy.
I must ask your indulgence for having merely selected a few out of the many possible views as regards the Problems of Inorganic Chemistry. I can only plead in excuse that my task is not an easy one; and I venture to express the hope that some light has been thrown on the shady paths which penetrate that dark region which we term the future.
- ↑ An address at the International Congress of Arts and Science, St. Louis, September, 1904.