 | CHEMISTRY SINCE THE TIME OF DALTON A History of Science |  |
3. CHEMISTRY SINCE THE TIME OF DALTON
JOHN DALTON AND THE ATOMIC THEORY
SMALL beginnings as have great endings—sometimes. As a case in point, note what came of the small, original effort of a self-trained back-country Quaker youth named John Dalton, who along towards the close of the eighteenth century became interested in the weather, and was led to construct and use a crude water-gauge to test the amount of the rainfall. The simple experiments thus inaugurated led to no fewer than two hundred thousand recorded observations regarding the weather, which formed the basis for some of the most epochal discoveries in meteorology, as we have seen. But this was only a beginning. The simple rain-gauge pointed the way to the most important generalization of the nineteenth century in a field of science with which, to the casual observer, it might seem to have no alliance whatever. The wonderful theory of atoms, on which the whole gigantic structure of modern chemistry is founded, was the logical outgrowth, in the mind of John Dalton, of those early studies in meteorology.
The way it happened was this: From studying the rainfall, Dalton turned naturally to the complementary process of evaporation. He was soon led to believe that
It was about the year 1803 that Dalton first gained a full grasp of the conception of the chemical atom. At once he saw that the hypothesis, if true, furnished a marvellous key to secrets of matter hitherto insoluble— questions relating to the relative proportions of the atoms themselves. It is known, for example, that a certain bulk of hydrogen gas unites with a certain bulk of oxygen gas to form water. If it be true that this combination consists essentially of the union of atoms one with another (each single atom of hydrogen united
Be that as it may, it is certain enough that Dalton's contemporaries were at first little impressed with the novel atomic theory. Just at this time, as it chanced, a dispute was waging in the field of chemistry regarding a matter of empirical fact which must necessarily be settled before such a theory as that of Dalton could even hope for a bearing. This was the question whether or not chemical elements unite with one another always
John Dalton
[Description: Portrait of John Dalton]But this contention of the master was most actively disputed, in particular by Louis Joseph Proust, and all chemists of repute were obliged to take sides with one or the other. For a time the authority of Berthollet held out against the facts, but at last accumulated evidence told for Proust and his followers, and towards the close of the first decade of our century it came to be generally conceded that chemical elements combine with one another in fixed and definite proportions.
More than that. As the analysts were led to weigh carefully the quantities of combining elements, it was observed that the proportions are not only definite, but that they bear a very curious relation to one another. If element A combines with two different proportions of element B to form two compounds, it appears that the weight of the larger quantity of B is an exact multiple of that of the smaller quantity. This curious relation was noticed by Dr. Wollaston, one of the most accurate of observers, and a little later it was confirmed by Johan Jakob Berzelius, the great Swedish chemist, who was to be a dominating influence in the chemical world for a generation to come. But this combination of elements in numerical proportions was exactly what Dalton had noticed as early as 1802, and what bad led him directly to the atomic weights. So the confirmation of
During these same years the rising authority of the French chemical world, Joseph Louis Gay-Lussac, was conducting experiments with gases, which he had undertaken at first in conjunction with Humboldt, but which later on were conducted independently. In 1809, the next year after the publication of the first volume of Dalton's New System of Chemical Philosophy, Gay-Lussac published the results of his observations, and among other things brought out the remarkable fact that gases, under the same conditions as to temperature and pressure, combine always in definite numerical proportions as to volume. Exactly two volumes of hydrogen, for example, combine with one volume of oxygen to form water. Moreover, the resulting compound gas always bears a simple relation to the combining volumes. In the case just cited, the union of two volumes of hydrogen and one of oxygen results in precisely two volumes of water vapor.
Naturally enough, the champions of the atomic theory seized upon these observations of Gay-Lussac as lending strong support to their hypothesis—all of them, that is, but the curiously self-reliant and self-sufficient author of the atomic theory himself, who declined to accept the observations of the French chemist as valid. Yet the observations of Gay-Lussac were correct, as countless chemists since then have demonstrated anew, and his theory of combination by volumes became one of the foundation-stones of the atomic theory, despite the opposition of the author of that theory.
The true explanation of Gay-Lussac's law of combination
This vastly important distinction between atoms and molecules, implied in the law just expressed, was published in 1811. Four years later, the famous French physicist Ampère outlined a similar theory, and utilized the law in his mathematical calculations. And with that the law of Avogadro dropped out of sight for a full generation. Little suspecting that it was the very key to the inner mysteries of the atoms for which they were seeking, the chemists of the time cast it aside, and let it fade from the memory of their science.
This, however, was not strange, for of course the law of Avogadro is based on the atomic theory, and in 1811 the atomic theory was itself still being weighed in the balance. The law of multiple proportions found general acceptance as an empirical fact; but many of the leading
At least two great chemists of the time, however, adopted the atomic view with less reservation. One of these was Thomas Thomson, professor at Edinburgh, who, in 1807, had given an outline of Dalton's theory in a widely circulated book, which first brought the theory to the general attention of the chemical world. The other and even more noted advocate of the atomic theory was Johan Jakob Berzelius. This great Swedish chemist at once set to work to put the atomic theory to such tests as might be applied in the laboratory. He was an analyst of the utmost skill, and for years be devoted himself to the determination of the combining weights, "equivalents" or "proportions," of the different elements. These determinations, in so far as they were accurately made, were simple expressions of empirical facts, independent of any theory; but gradually it became more and more plain that these facts all harmonize with the atomic theory of Dalton. So by common consent the proportionate combining weights of the elements came to be known as atomic weights—the name Dalton had given them from the first—and the tangible conception of the chemical atom as a body of definite constitution and weight gained steadily in favor.
From the outset the idea had had the utmost tangibility in the mind of Dalton. He had all along represented the different atoms by geometrical symbols— as a circle for oxygen, a circle enclosing a dot for hydrogen, and the like—and had represented compounds by placing these symbols of the elements in juxtaposition. Berzelius proposed to improve upon this method by substituting for the geometrical symbol the initial of the Latin name of the element represented— O for oxygen, H for hydrogen, and so on—a numerical coefficient to follow the letter as an indication of the number of atoms present in any given compound. This simple system soon gained general acceptance, and with slight modifications it is still universally employed. Every school-boy now is aware that H2O is the chemical way of expressing the union of two atoms of hydrogen with one of oxygen to form a molecule of water. But such a formula would have had no meaning for the wisest chemist before the day of Berzelius.
The universal fame of the great Swedish authority served to give general currency to his symbols and atomic weights, and the new point of view thus developed led presently to two important discoveries which removed the last lingering doubts as to the validity of the atomic theory. In 1819 two French physicists, Dulong and Petit, while experimenting with heat, discovered that the specific heats of solids (that is to say, the amount of heat required to raise the temperature of a given mass to a given degree) vary inversely as their atomic weights. In the same year Eilhard Mitscherlich, a German investigator, observed that compounds
Here, then, were two utterly novel and independent sets of empirical facts which harmonize strangely with the supposition that substances are composed of chemical atoms of a determinate weight. This surely could not be coincidence—it tells of law. And so as soon as the claims of Dulong and Petit and of Mitscherlich had been substantiated by other observers, the laws of the specific heat of atoms, and of isomorphism, took their place as new levers of chemical science. With the aid of these new tools an impregnable breastwork of facts was soon piled about the atomic theory. And John Dalton, the author of that theory, plain, provincial Quaker, working on to the end in semi-retirement, became known to all the world and for all time as a master of masters.
HUMPHRY DAVY AND ELECTRO-CHEMISTRY
During those early years of the nineteenth century, when Dalton was grinding away at chemical fact and theory in his obscure Manchester laboratory, another Englishman held the attention of the chemical world with a series of the most brilliant and widely heralded researches. This was Humphry Davy, a young man who had conic to London in 1801, at the instance of Count Rumford, to assume the chair of chemical philosophy in the Royal Institution, which the famous American had just founded.
Here, under Davy's direction, the largest voltaic battery yet constructed had been put in operation, and
What Davy really had done was to decompose the potash, which hitherto had been supposed to be elementary, liberating its oxygen, and thus isolating its metallic base, which he named potassium. The same thing was done with soda, and the closely similar metal sodium was discovered—metals of a unique type, possessed of a strange avidity for oxygen, and capable of seizing on it even when it is bound up in the molecules of water. Considered as mere curiosities, these discoveries were interesting, but aside from that they were of great theoretical importance, because they showed the compound nature of some familiar chemicals that had been regarded as elements. Several other elementary earths met the same fate when subjected to the electrical influence; the metals barium, calcium, and strontium being thus discovered. Thereafter Davy always referred to the supposed elementary substances (including oxygen, hydrogen, and the rest) as "unde-compounded" bodies. These resist all present efforts to decompose them, but how can one know what might not happen were they subjected to an influence, perhaps some day to be discovered, which exceeds the
Another and even more important theoretical result that flowed from Davy's experiments during this first decade of the century was the proof that no elementary substances other than hydrogen and oxygen are produced when pure water is decomposed by the electric current. It was early noticed by Davy and others that when a strong current is passed through water, alkalies appear at one pole of the battery and acids at the other, and this though the water used were absolutely pure. This seemingly told of the creation of elements—a transmutation but one step removed from the creation of matter itself—under the influence of the new "force." It was one of Davy's greatest triumphs to prove, in the series of experiments recorded in his famous Bakerian lecture of 1806, that the alleged creation of elements did not take place, the substances found at the poles of the battery having been dissolved from the walls of the vessels in which the water experimented upon had been placed. Thus the same implement which had served to give a certain philosophical warrant to the fading dreams of alchemy banished those dreams peremptorily from the domain of present science.
"As early as 1800," writes Davy, "I had found that when separate portions of distilled water, filling two glass tubes, connected by moist bladders, or any moist animal or vegetable substances, were submitted to the electrical action of the pile of Volta by means of gold wires, a nitro-muriatic solution of gold appeared in the tube containing the positive wire, or the wire transmitting the electricity, and a solution of soda in the opposite
"In cases when I had procured much soda, the glass at its point of contact with the wire seemed considerably corroded; and I was confirmed in my idea of referring the production of the alkali principally to this source, by finding that no fixed saline matter could be obtained by electrifying distilled water in a single agate cup from two points of platina with the Voltaic battery.
"Mr. Sylvester, however, in a paper published in Mr. Nicholson's journal for last August, states that though no fixed alkali or muriatic acid appears when a single vessel is employed, yet that they are both formed when two vessels are used. And to do away with all objections with regard to vegetable substances or glass, he conducted his process in a vessel made of baked tobacco-pipe clay inserted in a crucible of platina. I have no doubt of the correctness of his results; but the conclusion appears objectionable. He conceives, that he obtained fixed alkali, because the fluid after being heated and evaporated left a matter that tinged turmeric brown, which would have happened had it been lime, a substance that exists in considerable quantities in all pipe-clay; and even allowing the presence of fixed alkali,
"I resumed the inquiry; I procured small cylindrical cups of agate of the capacity of about one-quarter of a cubic inch each. They were boiled for some hours in distilled water, and a piece of very white and transparent amianthus that had been treated in the same way was made then to connect together; they were filled with distilled water and exposed by means of two platina wires to a current of electricity, from one hundred and fifty pairs of plates of copper and zinc four inches square, made active by means of solution of alum. After forty-eight hours the process was examined: Paper tinged with litmus plunged into the tube containing the transmitting or positive wire was immediately strongly reddened. Paper colored by turmeric introduced into the other tube had its color much deepened; the acid matter gave a very slight degree of turgidness to solution of nitrate of soda. The fluid that affected turmeric retained this property after being strongly boiled; and it appeared more vivid as the quantity became reduced by evaporation; carbonate of ammonia was mixed with it, and the whole dried and exposed to a strong heat; a minute quantity of white matter remained, which, as far as my examinations could go, had the properties of carbonate of soda. I compared it with similar minute portions of the pure carbonates of potash, and similar minute portions of the pure carbonates of potash and soda. It was not so deliquescent as the former of these bodies, and it formed a salt with nitric acid, which, like nitrate
"This result was unexpected, but it was far from convincing me that the substances which were obtained were generated. In a similar process with glass tubes, carried on under exactly the same circumstances and for the same time, I obtained a quantity of alkali which must have been more than twenty times greater, but no traces of muriatic acid. There was much probability that the agate contained some minute portion of saline matter, not easily detected by chemical analysis, either in combination or intimate cohesion in its pores. To determine this, I repeated this a second, a third, and a fourth time. In the second experiment turbidness was still produced by a solution of nitrate of silver in the tube containing the acid, but it was less distinct; in the third process it was barely perceptible; and in the fourth process the two fluids remained perfectly clear after the mixture. The quantity of alkaline matter diminished in every operation; and in the last process, though the battery had been kept in great activity for three days, the fluid possessed, in a very slight degree, only the power of acting on paper tinged with turmeric; but its alkaline property was very sensible to litmus paper slightly reddened, which is a much more delicate test; and after evaporation and the process by carbonate of ammonia, a barely perceptible quantity of fixed alkali was still left. The acid matter in the other tube was abundant; its taste was sour; it smelled like water over which large quantities of nitrous gas have been long kept; it did not effect solution of muriate of barytes; and a drop of it placed upon a polished
"After these results I could no longer doubt that some saline matter existing in the agate tubes had been the source of the acid matter capable of precipitating nitrate of silver and much of the alkali. Four additional repetitions of the process, however, convinced me that there was likewise some other cause for the presence of this last substance; for it continued to appear to the last in quantities sufficiently distinguishable, and apparently equal in every case. I had used every precaution, I had included the tube in glass vessels out of the reach of the circulating air; all the acting materials had been repeatedly washed with distilled water; and no part of them in contact with the fluid had been touched by the fingers.
"The only substance that I could now conceive as furnishing the fixed alkali was the water itself. This water appeared pure by the tests of nitrate of silver and muriate of barytes; but potash of soda, as is well known, rises in small quantities in rapid distillation; and the New River water which I made use of contains animal and vegetable impurities, which it was easy to conceive might furnish neutral salts capable of being carried over in vivid ebullition."1 Further experiment proved the correctness of this inference, and the last doubt as to the origin of the puzzling chemical was dispelled.
Though the presence of the alkalies and acids in the water was explained, however, their respective migrations to the negative and positive poles of the battery
This theory of binary composition of all chemical compounds, through the union of electro-positive and electro-negative atoms or molecules, was extended by Berzelius, and made the basis of his famous system of theoretical chemistry. This theory held that all inorganic compounds, however complex their composition, are essentially composed of such binary combinations. For many years this view enjoyed almost undisputed sway. It received what seemed strong confirmation when Faraday showed the definite connection between the amount of electricity employed and the amount of decomposition produced in the so-called electrolyte. But its claims were really much too comprehensive, as subsequent discoveries proved.
ORGANIC CHEMISTRY AND THE IDEA OF THE MOLECULE
When Berzelius first promulgated his binary theory he was careful to restrict its unmodified application to the compounds of the inorganic world. At that time,
Therefore a veritable sensation was created in the chemical world when, in the year 1828, it was announced that the young German chemist, Friedrich Wöhler, formerly pupil of Berzelius, and already known as a coming master, had actually synthesized the well-known organic product urea in his laboratory at Sacrow. The "exception which proves the rule" is something never heard of in the domain of logical science. Natural law knows no exceptions. So the synthesis of a single organic compound sufficed at a blow to break down the chemical barrier which the imagination of the fathers of the science had erected between animate and inanimate nature. Thenceforth the philosophical chemist would regard the plant and animal organisms as chemical laboratories in which conditions are peculiarly favorable for building up complex compounds of
Now a wave of interest in organic chemistry swept over the chemical world, and soon the study of carbon compounds became as much the fashion as electro-chemistry had been in the, preceding generation.
Foremost among the workers who rendered this epoch of organic chemistry memorable were Justus Liebig in Germany and Jean Baptiste André Dumas in France, and their respective pupils, Charles Frédéric Gerhardt and Augustus Laurent. Wöhler, too, must be named in the same breath, as also must Louis Pasteur, who, though somewhat younger than the others, came upon the scene in time to take chief part in the most important of the controversies that grew out of their labors.
Several years earlier than this the way had been paved for the study of organic substances by Gay-Lussac's discovery, made in 1815, that a certain compound of carbon and nitrogen, which he named cyanogen, has a peculiar degree of stability which enables it to retain its identity and enter into chemical relations after the manner of a simple body. A year later Ampère discovered that nitrogen and hydrogen, when combined in certain proportions to form what he called ammonium, have the same property. Berzelius had seized upon this discovery of the compound radical, as it was called, because it seemed to lend aid to his dualistic theory. He conceived the idea that all organic compounds are binary unions of various compound radicals
But even in the day of its seeming triumph the dualistic theory was destined to receive a rude shock. This came about through the investigations of Dumas, who proved that in a certain organic substance an atom of hydrogen may be removed and an atom of chlorine substituted in its place without destroying the integrity of the original compound—much as a child might substitute one block for another in its play-house. Such a substitution would be quite consistent with the dualistic theory, were it not for the very essential fact that hydrogen is a powerfully electro-positive element, while chlorine is as strongly electro-negative. Hence the compound radical which united successively with these two elements must itself be at one time electro-positive, at another electro-negative—a seeming inconsistency which threw the entire Berzelian theory into disfavor.
In its place there was elaborated, chiefly through the efforts of Laurent and Gerhardt, a conception of the molecule as a unitary structure, built up through the aggregation of various atoms, in accordance with "elective affinities" whose nature is not yet understood A doctrine of "nuclei" and a doctrine of "types" of molecular structure were much exploited, and, like the
CHEMICAL AFFINITY
Of course the atom itself was in no sense displaced, but Avogadro's law soon made it plain that the atom had often usurped territory that did not really belong to it. In many cases the chemists had supposed themselves dealing with atoms as units where the true unit was the molecule. In the case of elementary gases, such as hydrogen and oxygen, for example, the law of equal numbers of molecules in equal spaces made it clear that the atoms do not exist isolated, as had been supposed. Since two volumes of hydrogen unite with one volume of oxygen to form two volumes of water
What, then, does this imply? Why, that the elementary atom has an avidity for other atoms, a longing for companionship, an "affinity"—call it what you will—which is bound to be satisfied if other atoms are in the neighborhood. Placed solely among atoms of its own kind, the oxygen atom seizes on a fellow oxygen atom, and in all their mad dancings these two mates cling together—possibly revolving about each other in miniature planetary orbits. Precisely the same thing occurs among the hydrogen atoms. But now suppose the various pairs of oxygen atoms come near other pairs of hydrogen atoms (under proper conditions which need not detain us here), then each oxygen atom loses its attachment for its fellow, and flings itself madly into the circuit of one of the hydrogen couplets, and—presto!—there are only two molecules for every three there were before, and free oxygen and hydrogen have become water. The whole process, stated in chemical phraseology, is summed up in the statement that under the given conditions the oxygen atoms had a greater affinity for the hydrogen atoms than for one another.
As chemists studied the actions of various kinds of atoms, in regard to their unions with one another to
Evidently, then, one atom is not always equivalent to another atom of a different kind in combining powers. A recognition of this fact by Frankland about 1852, and its further investigation by others (notably A. Kekulé and A. S. Couper), led to the introduction of the word equivalent into chemical terminology in a new sense, and in particular to an understanding of the affinities or "valency" of different elements, which proved of the most fundamental importance. Thus it was shown that, of the four elements that enter most prominently into organic compounds, hydrogen can link itself with only a single bond to any other element —it has, so to speak, but a single hand with which to grasp—while oxygen has capacity for two bonds, nitrogen for three (possibly for five), and carbon for four. The words monovalent, divalent, trivalent, tretravalent,
But the molecule of water, on the other hand, has its atoms arranged in a state of stable equilibrium, all their affinities being satisfied. Each hydrogen atom has satisfied its own affinity by clutching the oxygen atom; and the oxygen atom has both its bonds satisfied by clutching back at the two hydrogen atoms. Therefore
But a consideration of this condition of stable equilibrium in the molecule at once suggests a new question: How can an aggregation of atoms, having all their affinities satisfied, take any further part in chemical reactions? Seemingly such a molecule, whatever its physical properties, must be chemically inert, incapable of any atomic readjustments. And so in point of fact it is, so long as its component atoms cling to one another unremittingly. But this, it appears, is precisely what the atoms are little prone to do. It seems that they are fickle to the last degree in their individual attachments, and are as prone to break away from bondage as they are to enter into it. Thus the oxygen atom which has just flung itself into the circuit of two hydrogen atoms, the next moment flings itself free again and seeks new companions. It is for all the world like the incessant change of partners in a rollicking dance. This incessant dissolution and reformation of molecules in a substance which as a whole remains apparently unchanged was first fully appreciated by Ste.-Claire Deville, and by him named dissociation. It is a process which goes on much more actively in some compounds than in others, and very much more actively under some physical conditions. (such as increase of
While, however, an appreciation of this ceaseless activity of the atom is essential to a proper understanding of its chemical efficiency, yet from another point of view the "saturated" molecule—that is, the molecule whose atoms have their valency all satisfied—may be thought of as a relatively fixed or stable organism. Even though it may presently be torn down, it is for the time being a completed structure; and a consideration of the valency of its atoms gives the best clew that has hitherto been obtainable as to the character of its architecture. How important this matter of architecture of the molecule—of space relations of the atoms—may be was demonstrated as long ago as 1823, when Liebig and Wöhler proved, to the utter bewilderment of the chemical world, that two substances may have precisely the same chemical constitution—the same number and kind of atoms—and yet differ utterly in physical properties. The word isomerism was coined by Berzelius to express this anomalous condition of things, which seemed to negative the most fundamental truths of chemistry. Naming the condition by no means explained it, but the fact was made clear that something besides the mere number and kind of atoms
How delicate may be the gradations of architectural design in building a molecule was well illustrated about 1850, when Pasteur discovered that some carbon compounds —as certain sugars—can only be distinguished from one another, when in solution, by the fact of their twisting or polarizing a ray of light to the left or to the right, respectively. But no inkling of an explanation of these strange variations of molecular structure came until the discovery of the law of valency. Then much of the mystery was cleared away; for it was plain that since each atom in a molecule can hold to itself only a fixed number of other atoms, complex molecules must have their atoms linked in definite chains or groups. And it is equally plain that where the atoms are numerous, the exact plan of grouping may sometimes be susceptible of change without doing violence to the law of valency. It is in such cases that isomerism is observed to occur.
By paying constant heed to this matter of the affinities, chemists are able to make diagrammatic pictures of the plan of architecture of any molecule whose composition is known. In the simple molecule of water (H2O), for example, the two hydrogen atoms must have released each other before they could join the oxygen, and the manner of linking must apparently be that represented in the graphic formula H—O—H. With molecules composed of a large number of atoms, such graphic representation of the scheme of linking is of
PERIODICITY OF ATOMIC WEIGHTS
These utterly novel studies of molecular architecture may seem at first sight to take from the atom much of its former prestige as the all-important personage of the chemical world. Since so much depends upon the mere position of the atoms, it may appear that comparatively little depends upon the nature of the atoms themselves. But such a view is incorrect, for on closer consideration it will appear that at no time has the atom been seen to renounce its peculiar personality. Within certain limits the character of a molecule may be altered by changing the positions of its atoms (just as different buildings may be constructed of the same bricks), but these limits are sharply defined, and it would be as impossible to exceed them as it would be to build a stone building with bricks. From first to last the brick remains a brick, whatever the style of architecture it helps to construct; it never becomes a stone. And just as closely does each atom retain its own peculiar properties, regardless of its surroundings.
Thus, for example, the carbon atom may take part in the formation at one time of a diamond, again of a piece
All this being true, it would seem as if the position of the Daltonian atom as a primordial bit of matter, indestructible and non-transmutable, had been put to the test by the chemistry of our century, and not found wanting. Since those early days of the century when the electric battery performed its miracles and seemingly reached its limitations in the hands of Davy, many new elementary substances have been discovered, but no single element has been displaced from its position as an undecomposable body. Rather have the analyses of the chemist seemed to make it more and more certain that all elementary atoms are in truth what John Herschel called them, "manufactured articles" —primordial, changeless, indestructible.
And yet, oddly enough, it has chanced that hand in hand with the experiments leading to such a goal have gone other experiments arid speculations of exactly the opposite tenor. In each generation there have been
Prout advanced this startling idea at first tentatively, in an anonymous publication; but afterwards he espoused it openly and urged its tenability. Coming just after Davy's dissociation of some supposed elements, the idea proved alluring, and for a time gained such popularity that chemists were disposed to round out the observed atomic weights of all elements into whole numbers. But presently renewed determinations of the atomic weights seemed to discountenance this practice, and Prout's alleged law fell into disrepute. It was revived, however, about 1840, by Dumas, whose
Subsequently Stas, the pupil of Dumas, undertook a long series of determinations of atomic weights, with the expectation of confirming the Proutian hypothesis. But his results seemed to disprove the hypothesis, for the atomic weights of many elements differed from whole numbers by more, it was thought, than the limits of error of the experiments. It was noteworthy, however, that the confidence of Dumas was not shaken, though he was led to modify the hypothesis, and, in accordance with previous suggestions of Clark and of Marignac, to recognize as the primordial element, not hydrogen itself, but an atom half the weight, or even one-fourth the weight, of that of hydrogen, of which primordial atom the hydrogen atom itself is compounded. But even in this modified form the hypothesis found great opposition from experimental observers.
In 1864, however, a novel relation between the weights of the elements and their other characteristics was called to the attention of chemists by Professor John A. R. Newlands, of London, who had noticed that if the elements are arranged serially in the numerical order of their atomic weights, there is a curious recurrence of similar properties at intervals of eight elements This so-called "law of octaves" attracted little immediate attention, but the facts it connotes soon came under the observation of other chemists, notably of Professors Gustav Hinrichs in America,
Though this early exposition of what has since been admitted to be a most important discovery was very fully outlined, the generality of chemists gave it little heed till a decade or so later, when three new elements, gallium, scandium, and germanium, were discovered, which, on being analyzed, were quite unexpectedly found to fit into three gaps which Mendelèeff had left in his periodic scale. In effect the periodic law had enabled Mendelèeff to predicate the existence of the new elements years before they were discovered. Surely a system that leads to such results is no mere vagary. So very soon the periodic law took its place as one of the most important generalizations of chemical science.
This law of periodicity was put forward as an expression of observed relations independent of hypothesis; but of course the theoretical bearings of these facts could not be overlooked. As Professor J. H. Gladstone has said, it forces upon us "the conviction that the elements are not separate bodies created without reference to one another, but that they have been originally fashioned, or have been built up, from one another, according to some general plan." It is but a short step from that proposition to the Proutian hypothesis.
NEW WEAPONS—SPECTROSCOPE AND CAMERA
But the atomic weights are not alone in suggesting the compound nature of the alleged elements. Evidence
To render the utility of the spectroscope complete, however, it was necessary to link with it another new chemical agency—namely, photography. This now familiar process is based on the property of light to decompose certain unstable compounds of silver, and thus alter their chemical composition. Davy and Wedgwood barely escaped the discovery of the value of the photographic method early in the nineteenth century. Their successors quite overlooked it until about 1826, when Louis J. M. Daguerre, the French chemist, took the matter in hand, and after many years of experimentation brought it to relative perfection in 1839, in which year the famous daguerreotype first brought the matter to popular attention. In the same year Mr. Fox Talbot read a paper on the subject before the Royal Society, and soon afterwards the efforts of Herschel and numerous other natural philosophers contributed to the advancement of the new method.
In 1843 Dr. John W. Draper, the famous English-American chemist and physiologist, showed that by photography the Fraunhofer lines in the solar spectrum might be mapped with absolute accuracy; also proving that the silvered film revealed many lines invisible to the unaided eye. The value of this method of observation was recognized at once, and, as soon as the spectroscope was perfected, the photographic method, in conjunction with its use, became invaluable to the chemist. By this means comparisons of spectra may be made with a degree of accuracy not otherwise obtainable; and, in case of the stars, whole clusters of spectra may be placed on record at a single observation.
As the examination of the sun and stars proceeded,
John W. Draper
[Description: Portrait of John W. Draper]In 1878 Professor J. Norman Lockyer, in a paper before the Royal Society, called attention to the possible significance of this series of observations. He urged that the fact of the sun showing fewer elements than are observed here on the cool earth, while stars much hotter than the sun show chiefly one element, and that one hydrogen, the lightest of known elements, seemed to give color to the possibility that our alleged elements are really compounds, which at the temperature of the hottest stars may be decomposed into hydrogen, the latter "element" itself being also doubtless a compound, which might be resolved under yet more trying conditions.
Here, then, was what might be termed direct experimental evidence for the hypothesis of Prout. Unfortunately, however, it is evidence of a kind which only a few experts are competent to discuss—so very delicate a matter is the spectral analysis of the stars. What is
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