1911 Encyclopædia Britannica/Element
ELEMENT (Lat. elementum), an ultimate component of anything, hence a fundamental principle. Elementum was used in Latin to translate the Greek στοιχεῖον (that which stands in a στοῖχος, or row), and is a word of obscure origin and etymology. The root of Lat. alere, to nourish, has been suggested, thus making it a doublet of alimentum, that which supports life; another explanation is that the word represents LMN., the first three letters of the second part of the alphabet, a parallel use to that of ABC. Apart from its application in chemistry, which is treated below, the word is used of the rudiments or principia of any science or subject, as in Euclid’s Elements of Geometry, or in the “beggarly elements” (τὰπτωχὰ στοιχεῖα, of St Paul in Gal. iv. 9); in mathematics, of a fundamental concept involved in an investigation, as the “elements” of a determinant; and in electricity, of a galvanic (or voltaic) “element” in an electric cell (see Battery: Electric). In astronomy, “element” is used of any one of the numerical or geometrical data by which the course of a varying phenomenon is computed; it is applied especially to orbital motion and eclipses. The “elements of an orbit” are the six data by which the position of a moving body in its orbit at any time may be determined. The “elements of an eclipse” express and determine the motion of the centre of the shadow-axis, and are the data necessary to compute the phenomena of an eclipse during its whole course, as seen at any place. In architecture the term “element” is applied to the outline of the design of a Decorated window, on which the centres for the tracery are found. These centres will all be found to fall on points which, in some way or other, will be equimultiples of parts of the openings.
Like all other scientific concepts, that of an element has changed its meaning many times in many ways during the development of science. Owing to their very small amount of real chemical knowledge, the generalizations of the ancients were necessarily rather superficial, Ancient ideas. and could not stand in the face of the increasing development of practical chemistry. Nevertheless we find the concept of an element as “a substance from which all bodies are made or derived” held at the very beginning of occidental philosophy. Thales regarded “water” as the element of all things; his followers accepted his idea of a primordial substance as the basis of all bodies, but they endeavoured to determine some other general element or elements, like “fire” or “spirit,” or “love” and “hatred,” or “fire,” “water,” “air” and “earth.” We find in this development an exact parallelism to the manner in which scientific ideas generally arise, develop and change. They are created to point out the common part in a variety of observed phenomena, in order to get some leading light in the chaos of events. At first almost any idea will do, if only it promises some comprehensive arrangement of the facts; afterwards, the inconsistencies of the first trial make themselves felt; the first idea is then changed to meet better the new requirements. For a shorter or longer time the facts and ideas may remain in accord, but the uninterrupted increase of empirical knowledge involves sooner or later new fundamental alterations of the general idea, and in this way there is a never-ceasing process of adaptation of the ideas to the facts. As facts are unchangeable by themselves, the adaptation can be only one-sided; the ideas are compelled to change according to the facts. We must therefore educate ourselves to regard the ideas or theories as the changing part of science, and keep ourselves ready to accept even the most fundamental revision of current theories.
The first step in the development of the idea of elements was to recognize that a single principle would not prove sufficient to cover the manifoldness of facts. Empedocles therefore conceived a double or binary elementary principle; and Aristotle developed this idea a stage further, stating two sets of binary antagonistic principles, namely “dry-wet” and “hot-cold.” The Aristotelian or peripatetic elements, which played such a great rôle in the whole medieval philosophy, are the representatives of the several binary combinations of these fundamental properties, “fire” being hot and dry, “air” hot and wet, “water” cold and wet, “earth” cold and dry. According to the amount of these properties found in any body, these elements were regarded as having taken part in forming this body. Concerning the reason why only these properties were regarded as fundamental, we know nothing. They seem to be taken at random rather than carefully selected; they relate only to the sense of touch, and not to vision or any other sense, possibly because deceptions in the sense of touch were regarded as non-existent, while the other senses were apparently not so trustworthy. At any rate, the Aristotelian elements soon proved to be rather inadequate to meet the requirements of the increasing chemical knowledge; other properties had therefore to be selected to represent the general behaviour of chemical substances, and in this case we find them already much more “chemical” in the modern sense.
Among the various substances recognized by the chemists, certain classes or groups readily distinguished themselves. First the metals, by their lustre, their heaviness, and a number of other common properties. According to the general principle of selecting a single substance Elements of the alchemists. as a representative of the group, the metallic properties were represented by “mercury.” The theoreticians of the middle ages were rather careful to point out that common mercury (the liquid metal of to-day) was not at all to be identified with “philosophical” mercury, the last being simply the principle of metallic behaviour. In the same way combustibility was represented by “sulphur,” solubility by “salt,” and occasionally the chemically indifferent or refractory character by “earth.” According to the subsistence and preponderance of these properties in different bodies, these were regarded as containing the corresponding elements; conversely, just as experience teaches the chemist every day that by proper treatment the properties of given bodies may be changed in the most various ways, the observed changes of properties were ascribed to the gain or loss of the corresponding elements. According to this theory, which accounted rather well for a large number of facts, there was no fundamental objection against trying to endow base metals with the properties of the precious ones; to make artificial gold was a task quite similar to the modern problem of, e.g. making artificial quinine. The realization that there is a certain natural law preventing such changes is of much later date. It is therefore quite unjust to consider the work of the alchemists, who tried to make artificial gold, as consummate nonsense. A priori there was no reason why a change from lead to gold should be less possible than a change from iron to rust; indeed there is no a priori reason against it now. But experience has taught us that lead and gold are chemical elements in the modern sense, and that there is a general experimental law that elements are not transformable one into another. So experience taught the alchemists irresistibly that in spite of the manifoldness of chemical changes it is not always possible to change any given substance into another; the possibilities are much more limited, and there is only a certain range of substances to be obtained from a given one. The impossibility of transforming lead or copper into noble metals proved to be only one case out of many, and it was recognized generally that there are certain chemical families whose members are related to one another by their mutual transformability, while it is impossible to bridge the boundaries separating these families.
The man who brought all these experiences and considerations into scientific form was Robert Boyle. He stated as a general principle, that only tangible and ponderable substances should be recognized as elements, an element being a substance from which other substances may be made, Work of Robert Boyle. but which cannot be separated into different substances. He showed that neither the peripatetic nor the alchemistic elements satisfied this definition. But he was more of a critical than of a synthetical turn of mind; although he established the correct principles, he hesitated to point out what substances, among those known at his time, were to be considered as elements. He only paved the way to the goal by laying the foundations of analytical chemistry, i.e. by teaching how to characterize and to distinguish different chemical individuals. Further, by adopting and developing the corpuscular hypothesis of the constitution of the ponderable substances, he foreshadowed, in a way, the law of the conservation of the elements, viz. that no element can be changed into another element; and he considered the compound substances to be made up from small particles or corpuscles of their elements, the latter retaining their essence in all combinations. This hypothesis accounts for the fact that only a limited number of other substances can be made from a given one—namely, only those which contain the elements present in the given substance. But it is characteristic of Boyle’s critical mind that he did not shut his eyes against a serious objection to his hypothesis. If the compound substance is made up of parts of the elements, one would expect that the properties of the compound substance would prove to be the sum of the properties of the elements. But this is not the case, and chemical compounds show properties which generally differ very considerably from those of the compounds. On the one hand, the corpuscular hypothesis of Boyle was developed into the atomic hypothesis of Dalton, which was considered at the beginning of the 19th century as the very best representation of chemical facts, while, on the other hand, the difficulty as to the properties of the compounds remained the same as Boyle found it, and has not yet been removed by an appropriate development of the atomic hypothesis. Thus Boyle considered, e.g. the metals as elements. However, it is interesting to note that he considered the mutual transformation of the metals as not altogether impossible, and he even tells of a case when gold was transformed into base metal. It is a common psychological fact that a reformer does not generally succeed in being wholly consistent in his reforming ideas; there remains invariably some point where he commits exactly the same fault which he set out to abolish. We shall find the same inconsistency also among other chemical reformers. Even earlier than Boyle, Joachim Jung (1587–1657) of Hamburg developed similar ideas. But as he did not distinguish himself, as Boyle did, by experimental work in science, his views exerted only a limited influence amongst his pupils.
In the times following Boyle’s work we find no remarkable outside development of the theory of elements, but a very important inside one. Analytical chemistry, or the art of distinguishing different chemical substances, was rapidly developing, and the necessary foundation for such a theory was thus Phlogiston theory. laid. We find the discussions about the true elements disappearing from the text-books, or removed to an insignificant corner, while the description of observed chemical changes of different ways of preparing the same substance, as identified by the same properties, and of the methods for recognizing and distinguishing the various substances, take their place. The similarity of certain groups of chemical changes, as, for example, combustion, and the inverse process, reduction, was observed, and thus led to an attempt to shape these most general facts into a common theory. In this way the theory of “phlogiston” was developed by G. E. Stahl, phlogiston being (according to the usual way of regarding general properties as being due to a principle or element) the “principle of combustibility,” similar to the “sulphur” of the alchemists. This again must be regarded as quite a legitimate step justified by the knowledge of the time. For experience taught that combustibility could be transferred by chemical action, e.g. from charcoal to litharge, the latter being changed thereby into combustible metallic lead; and according to Boyle’s principle, that only bodies should be recognized as chemical elements, phlogiston was considered as a body. From the fact that all leading chemists in the second half of the 18th century used the phlogiston theory and were not hindered by it in making their great discoveries, it is evident that a sufficient amount of truth and usefulness was embodied in this theory. It states indeed quite correctly the mutual relations between oxidation and reduction, as we now call these very general processes, and was erroneous only in regard to one question, which at that time had not aroused much interest, the question of the change of weight during chemical processes.
It was only after Isaac Newton’s discovery of universal gravitation that weight was considered as a property of paramount interest and importance, and that the question of the changes of weight in chemical reactions became one worth asking. When in due time this question was Lavoisier’s reform. raised, the fact became evident at once, that combustion means not loss but gain of weight. To be sure of this, it was necessary to know first the chemical and physical properties of gases, and it was just at the same time that this knowledge was developed by Priestley, Scheele and others. Lavoisier was the originator and expounder of the necessary reform. Oxygen was just discovered at that time, and Lavoisier gathered evidence from all sides that the theory of phlogiston had to be turned inside out to fit the new facts.
He realized that the sum total of the weights of all substances concerned within a chemical change is not altered by the change. This principle of the “conservation of weight” led at once to a simple and unmistakable definition of a chemical element. As the weight of a compound substance is the sum of the weights of its elements, the compound necessarily weighs more than any of its elements. An element is therefore a substance which, by being changed into another substance, invariably increases its weight, and never gives rise to substances of less weight. By the help of this criterion Lavoisier composed the first table of chemical elements similar to our modern ones. According to the knowledge of his time he regarded the alkalis as elements, although he remarked that they are rather similar to certain oxides, and therefore may possibly contain oxygen; the truth of this was proved at a later date by Humphry Davy. But the inconsistency of the reformer, already referred to, may be observed with Lavoisier. He included “heat and light” in his list of elements, although he knew that neither of them had weight, and that neither fitted his definition of an element; this atavistic survival was subsequently removed from the table of the elements by Berzelius in the beginning of the 19th century. In this way the question of what substances are to be regarded as chemical elements had been settled satisfactorily in a qualitative way, but it is interesting to realize that the last step in this development, the theory of Lavoisier, was based on quantitative considerations. Such considerations became of paramount interest at once, and led to the concept of the combining weights of the elements.
The first discoveries in this field were made in the last quarter of the 18th century by J. B. Richter. The point at issue was a rather commonplace one: it was the fact that when two neutral salt solutions were mixed to undergo mutual chemical decomposition and recombination, the resulting J. B. Richter’s work. liquid was neutral again, i.e. it did not contain any excess of acid or base. In other words, if two salts, A′B′ and A″ B″, composed of the acids A′ and A″ and the bases B′ and B″, undergo mutual decomposition, the amount of the base B′ left by the first salt, when its acid A′ united with the base B″ to form a new salt A′B″, was just enough to make a neutral salt A″B′ with the acid A″ left by the second salt. At first sight this looks quite simple and self-evident,—that neutral salts should form neutral ones again and not acid or basic ones,—but if this fact is once stated very serious quantitative inferences may be drawn from it, as Richter showed. For if the symbols A′, A″, B′, B″ denote at the same time such quantities of the acids and bases as form neutral salts, then if three of these quantities are determined, the fourth may be calculated from the others. This follows from the fact that by decomposing A′B′ with just the proper amount of the other salt to form A′B″, the remaining quantities B′ and A″ exist in exactly the ratio to form a neutral salt A″ B′. It is possible, therefore, to ascribe to each acid and base a certain relative weight or “combining weight” by which they will combine one with the other to form neutral salts. The same reasoning may be extended to any number of acids and bases.
It is true that Richter did not find out by himself this simplest statement of the law of neutrality which he discovered, but he expressed the same consequence in a rather clumsy way by a table of the combining weights of different bases related to the unit amount of a certain acid, and doing the same thing for the unit weight of every other acid. Then he observed that the numbers in these different tables are proportionate one to another. The same holds good if the corresponding series of the combining weights of acids for unit weights of different bases were tabulated. It was only a little later that a Berlin physicist, G. E. Fischer, united the whole system of Richter’s numbers simply into a double table of acids and bases, taking as unit an arbitrarily chosen substance, namely sulphuric acid. The following table by Fischer is therefore the first table of combining weights.
It is interesting again to notice how difficult it is for the discoverer of a new truth to find out the most simple and complete statement of his discovery. It looks as if the amount of work needed to get to the top of a new idea is so great that not enough energy remains to clear the very last few steps. It is noteworthy also to observe how difficult it was for the chemists of that time to understand the bearing of Richter’s work. Although a summary of his results was published in Berthollet’s Essai de statique chimique, one of the most renowned chemical books of that time, nobody dared for a long time to take up the scientific treasure laid open for all the world.
At the beginning of the 19th century the same question was taken up from quite another standpoint. John Dalton, in his investigations of the behaviour of gases, and in order to understand more easily what happened when gases were absorbed by liquids, used the corpuscular hypothesis John Dalton’s atomic theory. already mentioned in connexion with Boyle. While he depicted to himself how the corpuscles, or, as he preferred to call them, the “atoms” of the gases, entered the interstices of the atoms of the liquids in which they dissolved, he asked himself: Are the several atoms of the same substance exactly alike, or are there differences as between the grains of sand? Now experience teaches us that it is impossible to separate, for example, a quantity of pure water into two samples of somewhat different properties. When a pure substance is fractionated by partial distillation or partial crystallization or partial change into another substance by chemical means, we find constantly that the residue is not changed in its properties, as it would be if the atoms were slightly different, since in that case e.g. the lighter atoms would distil first and leave behind the heavier ones, &c. Therefore we must conclude that all atoms of the same kind are exactly alike in shape and weight. But, if this be so, then all combinations between different atoms must proceed in certain invariable ratios of the weights of the elements, namely by the ratio of the weights of the atoms. Now it is impossible to weigh the atoms directly; but if we determine the ratio of the weights in which oxygen and hydrogen combine to form water, we determine in this way also the relative weight of their atoms. By a proper number of analyses of simple chemical compounds we may determine the ratios between the weights of all elementary atoms, and, selecting one of them as a standard or unit, we may express the weight of all other atoms in terms of this unit. The following table is Dalton’s (Mem. of the Lit. and Phil. Soc. of Manchester (II.), vol. i. p. 287, 1805).
Table of the Relative Weights of the Ultimate Particles of Gaseous and
|Phosphuretted hydrogen||8.2||Sulphuric acid||25.4|
|Nitrous gas||9.3||Carburetted hydrogen from|
|Gaseous oxide of carbone||9.8||Olefiant gas||5.3|
Dalton at once drew a peculiar inference from this view. If two elements combine in different ratios, one must conclude that different numbers of atoms unite. There must be, therefore, a simple ratio between the quantities of the one element united to the same quantity of the other. Dalton showed at once that the analysis of carbon monoxide and of carbonic acid satisfied this consequence, the quantity of oxygen in the second compound being double the quantity in the first one. A similar relation holds good between marsh gas and olefiant gas (ethylene). This is the “law of multiple proportions” (see Atom). By these considerations Dalton extended the law of combining weights, which Richter had demonstrated only for neutral salts, to all possible chemical compounds. While the scope of the law was enormously extended, its experimental foundation was even smaller than with Richter. Dalton did not concern himself very much with the experimental verification of his ideas, and the first communication of his theory in a paper on the absorption of gases by liquids (1803) attracted as little notice as Richter’s discoveries. Even when T. Thomson published Dalton’s views in an appendix to his widely read text-book of chemistry, matters did not change very much. It was only by the work of J. J. Berzelius that the enormous importance of Dalton’s views was brought to light.
Berzelius was at that time busy in developing a trustworthy
system of chemical analysis, and for this purpose he investigated
the composition of the most important salts. He then
went over the work of Richter, and realized that by his
law he could check the results of his analyses. He tried
Berzelius. it and found the law to hold good in most cases; when it did not, according to his analyses, he found that the error was on his own side and that better analyses fitted Richter’s law. Thus he was prepared to understand the importance of Dalton’s views and he proceeded at once to test its exactness. The result was the best possible. The law of the combining weights of the atoms, or of the atomic weights, proved to hold good in every case in which it was tested. All chemical combinations between the several elements are therefore regulated by weight according to certain numbers, one for each element, and combinations between the elements occur only in ratios given by these weights or by simple multiples thereof. Consequently Berzelius regarded Dalton’s atomic hypothesis as proved by experiment, and became a strong believer in it.
At the same time W. H. Wollaston had discovered independently the law of multiple proportions in the case of neutral and acid salts. He gave up further work when he learned of Dalton’s ideas, but afterwards he pointed out that it was necessary to distinguish the hypothetical part in Dalton’s views from their empirical part. The latter is the law of combining weights, or the law that chemical combination occurs only according to certain numbers characteristic for each element. Besides this purely experimental law there is the hypothetical explanation by the assumption of the existence of atoms. As it is not proved that this explanation is the only one possible, the existence of the law is not a proof of the existence of the atoms. He therefore preferred to call the characteristic combining numbers of the elements not “atomic weights” but “chemical equivalents.”
Although there were at all times chemists who shared Wollaston’s cautious views, the atomic hypothesis found general acceptance because of its ready adaptability to the most diverse chemical facts. In our time it is even rather difficult to separate, as Wollaston did, the empirical part from the hypothetical one, and the concept of the atom penetrates the whole system of chemistry, especially organic chemistry.
If we compare the work of Dalton with that of Richter we find a fundamental difference. Richter’s inference as to the existence of combining weights in salts is based solely on an experimental observation, namely, the persistence of neutrality after double decomposition; Dalton’s theory, on the contrary, is based on the hypothetical concept of the atom. Now, however favourably one may think of the probability of the existence of atoms, this existence is really not an observed fact, and it is necessary therefore to ask: Does there exist some general fact which may lead directly to the inference of the existence of combining weights of the elements, just as the persistence of neutrality leads to the same consequence as to acids and bases? The answer is in the affirmative, although it took a whole century before this question was put and answered. In a series of rather difficult papers (Zeits. f. Phys. Chem. since 1895, and Annalen der Naturphilosophie since 1902), Franz Wald (of Kladno, Bohemia) developed his investigations as to the genesis of this general law. Later, W. Ostwald (Faraday lecture, Trans. Chem. Soc., 1904) simplified Wald’s reasoning and made it more evident.
The general fact upon which the necessary existence of combining weights of the elements may be based is the shifting character of the boundary between elements and compounds. It has already been pointed out that Lavoisier considered the alkalis and the alkaline earths as elements, because in his time they had not been decomposed. As long as the decomposition had not been effected, these compounds could be considered and treated like elements without mistake, their combining weight being the sum of the combining weights of their (subsequently discovered) elements. This means that compounds enter in reaction with other substances as a whole, just as elements do. In particular, if a compound AB combines with another substance (elementary or compound) C to form a ternary compound ABC, it enters this latter as a whole, leaving behind no residue of A or B. Inversely, if a ternary compound ABC be changed into a binary one AB by taking away the element C, there will not be found any excess of A or B, but both elements will exhibit just the same ratio in the binary as in the ternary compound.
Experimentally this important fact was proved first by Berzelius, who showed that by oxidizing lead sulphide, PbS, to lead sulphate, PbSO4, no excess either of sulphur or lead could be found after oxidation; the same held good with barium sulphite, BaSO3, when converted into barium sulphate, BaSO4. On a much larger scale and with very great accuracy the inverse was proved half a century later by J. S. Stas, who reduced silver chlorate, AgClO3, silver bromate, AgBrO3, and silver iodate, AgIO3, to the corresponding binary compounds, AgCl, AgBr and AgI, and searched in the residue of the reaction for any excess of silver or halogen. As the tests for these substances are among the most sensitive in analytical chemistry, the general law underwent a very severe test indeed. But the result was the same as was found by Berzelius—no excess of one of the elements could be discovered. We may infer, therefore, generally that compounds enter ulterior combinations without change of the ratio of their elements, or that the ratio between different elements in their compounds is the same in binary and ternary (or still more complicated) combinations.
This law involves the existence of general combining weights just in the same way as the law of neutrality with double decomposition of salts involves the law of the combining weights of acids and bases. For if the ratio between A and B is determined, this same ratio must obtain in all ternary and more complicated compounds, containing the same elements. The same is true for any other elements, C, D, E, F, &c., as related to A. But by applying the general law to the ternary compound ABC the same conclusion may be drawn as to the ratio A : C in all compounds containing A and C, or B : C in the corresponding compounds. By reasoning further in the same way, we come to the conclusion that only such compounds are possible which contain elements according to certain ratio-numbers, i.e. their combining weight. Any other ratio would violate the law of the integral reaction of compounds.
As to the law of multiple proportions, it may be deduced by a similar reasoning by considering the possible combinations between a compound, e.g. AB, and one of its elements, say B. AB and B can combine only according to their combining weights, and therefore the quantity of B combining with AB is equal to the quantity of AB which has combined with A to form AB. The new combination is therefore to be expressed by AB2. By extending this reasoning in the same way, we get the general conclusion that any compounds must be composed according to the formula AmBnCp..., where m, n, p, &c., are integers.
The bearing of these considerations on the atomic hypothesis is not to disprove it, but rather to show that the existence of the law of combining weights, which has been considered for so long as a proof of the truth of this hypothesis, does not necessarily involve such a consequence. Whether atoms may prove to exist or not, the law of combining weights is independent thereof.
Two problems arose from the discoveries of Dalton and Berzelius. The first was to determine as exactly as possible the correct numbers of the combining weights. The other results from the fact that the same elements may combine in different ratios. Which of these ratios Atomic weight determina-tions. gives the true ratio of the atomic weights? And which is the multiple one? Both questions have had most ample experimental investigation, and are now answered rather satisfactorily. The first question was a purely technical one; its answer depended upon analytical skill, and Berzelius in his time easily took the lead, his numbers being readily accepted on the continent of Europe. In England there was a certain hesitation at first, owing to Prout’s assumption (see below), but when Turner, at the instigation of the British Association for the Advancement of Science, tested Berzelius’s numbers and found them entirely in accordance with his own measurements, these numbers were universally accepted. But then a rather large error in one of Berzelius’s numbers (for carbon) was discovered in 1841 by Dumas and Stas, and a kind of panic ensued. New determinations of the atomic weights were undertaken from all sides. The result was most satisfactory for Berzelius, for no other important error was discovered, and even Dumas remarked that repeating a determination by Berzelius only meant getting the same result, if one worked properly. In later times more exact measurements, corresponding to the increasing art in analysis, were carried out by various workers, amongst whom J. S. Stas distinguished himself. But even the classical work of Stas proved not to be entirely without error; for every period has its limit in accuracy, which extends slowly as science extends. In recent times American chemists have been especially prominent in work of this kind, and the determinations of E. W. Morley, T. W. Richards and G. P. Baxter rank among the first in this line of investigation.
During this work the question arose naturally: How far does the exactness of the law extend? It is well known that most natural laws are only approximations, owing to disturbing causes. Are there disturbing causes also with atomic weights? The answer is that as far as we know there are none. The law is still an exact one. But we must keep in mind that an absolute answer is never possible. Our exactness is in every case limited, and as long as the possible variations lie behind this limit, we cannot tell anything about them. In recent times H. Landolt has doubted and experimentally investigated the law of the conservation of weight.
Landolt’s experiments were carried out in vessels of the shape of an inverted U, each branch holding one of the substances to react one on the other. Two vessels were prepared as equal as possible and hung on both sides of a most sensitive balance. Then the difference of weight was determined in the usual way by exchanging both the vessels on the balance. After this set of weighings one of the vessels was inverted and the chemical reaction between the contained substances was performed; then the double weighing was repeated. Finally also the second vessel was inverted and a third set of weighings taken. From blank experiments where the vessels were filled with substances which did not react one on the other, the maximum error was determined to 0.03 milligramme. The reactions experimented with were: silver salts with ferrous sulphate; iron on copper sulphate; gold chloride and ferrous chloride; iodic acid and hydriodic acid; iodine and sodium sulphite; uranyl nitrate and potassium hydrate; chloral hydrate and potassium hydrate; electrolysis of cadmium iodide by an alternating current; solution of ammonium chloride, potassium bromide and uranyl nitrate in water, and precipitation of an aqueous solution of copper sulphate by alcohol. In most of these experiments a slight diminution of weight was observed which exceeded the limit of error distinctly in two cases, viz. silver nitrate with ferrous sulphate and iodic acid with hydriodic acid, the loss of weight amounting from 0.068 to 0.199 mg. with the first and 0.047 to 0.177 mg. with the second reaction on about 50 g. of substance. As each of these reactions had been tried in nine independent experiments, Landolt felt certain that there was no error of observation involved. But when the vessels were covered inside with paraffin wax, no appreciable diminution of weight was observed.
These experiments apparently suggested a small decrease of weight as a consequence of chemical processes. On repeating them, however, and making allowance for the different amounts of water absorbed on the surface of the vessel at the beginning and end of the experiment, Landolt found in 1908 (Zeit. physik. Chem. 64, p. 581) that the variations in weight are equally positive and negative, and he concluded that there was no change in weight, at least to the extent of 1 part in 10,000,000.
There is still another question regarding the numerical values of the atomic weights, namely: Are there relations between the numbers belonging to the several elements? Richter had arranged his combining weights according to their magnitude, and endeavoured The periodic arrange-ment. to prove that they form a certain mathematical series. He also explained the incompleteness of his series by assuming that certain acids or bases requisite to the filling up of the gaps in the series, were not yet known. He even had the satisfaction that in his time a new base was discovered, which fitted rather well into one of his gaps; but when it turned out afterwards that this new base was only calcium phosphate, this way of reasoning fell into discredit and was resumed only at a much later date.
To obtain a correct table of atomic weights the second question already mentioned, viz. how to select the correct value in the case of multiple proportions, had to be answered. Berzelius was constantly on the look-out for means to distinguish the true atomic weights from their multiples or sub-multiples, but he could not find an unmistakable test. The whole question fell into a terrible disorder, until in the middle of the 19th century S. Cannizzaro showed that by taking together all partial evidences one could get a system of atomic weights consistent in itself and fitting the exigencies of chemical systematics. Then a startling discovery was made by the same method which Richter had tried in vain, by arranging all atomic weights in one series according to their numerical values.
The Periodic Law.—The history of this discovery is rather long. As early as 1817 J. W. Döbereiner of Jena drew attention to the fact that the combining weight of strontium lies midway between those of calcium and barium, and some years later he showed that such “triads” occurred in other cases too. L. Gmelin tried to apply this idea to all elements, but he realized that in many cases more than three elements had to be grouped together. While Ernst Lenssen applied the idea of triads to the whole table of chemical elements, but without any important result, the other idea of grouping more than three elements into series according to their combining weights proved more successful. It was the concept of homologous series just developed in organic chemistry which influenced such considerations. First Max von Pettenkofer in 1850 and then J. B. A. Dumas in 1851 undertook to show that such a series of similar elements could be formed, having nearly constant differences between their combining weights. It is true that this idea in all its simplicity did not hold good extensively enough; so J. P. Cooke and Dumas tried more complicated types of numerical series, but only with a temporary success.
The idea of arranging all elements in a single series in the order of the magnitude of their combining weights, the germ of which is to be found already in J. B. Richter’s work, appears first in 1860 in some tables published by Lothar Meyer for his lectures. Independently, A. E. B. de Chancourtois in 1862, J. A. R. Newlands in 1863, and D. I. Mendeléeff in 1869, developed the same idea with the same result, namely, that it is possible to divide this series of all the elements into a certain number of very similar parts. In their papers, which appeared in the same year, 1869, Lothar Meyer and Mendeléeff gave to all these trials the shape now generally adopted. They succeeded in proving beyond all doubt that this series was of a periodic character, and could be cut into shorter pieces of similar construction. Here again gaps were present to be filled up by elements to be discovered, and Mendeléeff, who did this, predicted from the general regularity of his table the properties of such unknown elements. In this case fate was more kind than with Richter, and science had the satisfaction of seeing these predictions turn out to be true.
The following table contains this periodic arrangement of the elements according to their atomic weight. By cutting the whole series into pieces of eight elements (or more in several cases) and arranging these one below another in the alternating way shown in the table, one finds similar elements placed in vertical series whose properties change gradually and with some regularity according to their place in the table. Not only the properties of the uncombined elements obey this rule, but also almost all properties of similar compounds of the elements.
|He 4.0||Li 7.03||Be 9.1||B 11.0||C 12.00||N 14.01||O 16.00||F 19.0||..||..||..|
|Ne 20||Na 23.00||Mg 24.32||Al 27.1||Si 28.4||P 31.0||S 32.06||Cl 35.45||..||..||..|
|Ar 39.9||K 39.15||Ca 40.1||Sc 44.1||Ti 48.1||V 51.2||Cr 52.0||Mn 55.0||Fe 55.9,||Ni 58.7,||Co 59.0|
|..||Cu 63.6||In 65.4||Ga 70||Ge 72.5||As 75.0||Se 79.2||Br 79.96||..||..||..|
|Kr 83.0||Rb 85.5||Sr 87.6||Y 89.0||Zr 90.6||Cb(Nb) 94||Mo 96.0||..||Ru 101.7,||Rh 103.0,||Pd 106.5|
|..||Ag 107.93||Cd 112.4||In 115||Sn 119.0||Sb 120.2||Te 127.6||I 126.97||..||..||..|
|Xe 130.7||Cs 132.9||Ba 137.4||La 138.9||Ce &c. 140||Ta 181||W 184||..||Os 191,||Ir 193.0,||Pt 194.8|
|..||Au 197.2||Hg 200.0||Tl 204.1||Pb 206.9||Bi 208.0||..||..||..||..||..|
|..||..||Ra 225||..||Th 232.5||..||U 238.5||..||..||..||..|
regularities can be called only rules, and not laws. In the first line one would expect that the steps in the values of the atomic weights should be regular, but it is not so. There are even cases when it is necessary to invert the order of the atomic weights to satisfy the chemical necessities. Thus argon has a larger number than potassium, but must precede it to fit into its proper place. The same is true of tellurium and iodine. It looks as if the real elements were scattered somewhat haphazard on a regular table, or as if some independent factor were active to disturb an existing regularity. It may be that the new facts mentioned above will lead also to an explanation of these irregularities; at present we must recognize them and not try to explain them away. Such considerations have to be kept in mind especially in regard to the very numerous attempts to express the series of combining weights in a mathematical form. In several cases rather surprising agreements were found, but never without exception. It looks as if some very important factor regulating the whole matter is still unknown, and before this has been elucidated no satisfactory treatment of the matter is possible. It seems therefore premature to enter into the details of these speculations.
In recent times not only our belief in the absolute exactness of the law of the conservation of weight has been shaken, but also our belief in the law of the conservation of the elements. The wonderful substance radium, whose Transmu-tation of elements. existence has made us to revise quite a number of old and established views, seems to be a fulfilment of the old problem of the alchemists. It is true that by its help lead is not changed into gold, but radium not only changes itself into another element, helium (Ramsay), but seems also to cause other elements to change. Work in this line is of present day origin only and we do not know what new laws will be found to regulate these most unexpected reactions (see Radioactivity). But we realize once more that no law can be regarded as free from criticism and limitation; in the whole realm of exact sciences there is no such thing as the Absolute.
Another question regarding the values of atomic weights was raised very soon after their first establishment. From the somewhat inexact first determinations William Prout concluded that all atomic weights are multiples of the atomic weight of hydrogen, thus suggesting all other Prout’s assumption. elements to be probably made up from condensed hydrogen. Berzelius found his determinations not at all in accordance with this assumption, and strongly opposed the arbitrary rounding off of the numbers practised by the partisans of Prout’s hypothesis. His hypothesis remained alive, although almost every chemist who did exact atomic weight determinations, especially Stas, contradicted it severely. Even in our time it seems to have followers, who hope that in some way the existing experimental differences may disappear. But one of the most important and best-known relations, that between hydrogen and oxygen, is certainly different from the simple ratio 1 : 16, for it has been determined by a large number of different investigators and by different methods to be undoubtedly lower, namely, 1 : 15.87. Therefore, if Prout’s hypothesis contain an element of truth, by the act of condensation of some simpler substance into the present chemical elements a change of weight also must have occurred, such that the weight of the element did not remain exactly the weight of the simpler substance which changed into it. We have already remarked that such phenomena are not yet known with certainty, but they cannot be regarded as utterly impossible.
It may here be mentioned that the internationality of science has shown itself active also in the question of atomic weights. These numbers undergo incessantly small variations because of new work done for their determination. To avoid the uncertainty arising from this inevitable International table of atomic weights. state of affairs, an international committee was formed by the co-operation of the leading chemical societies all over the world, and an international table of the most probable values is issued every year. The following table is that for 1910:—
O = 16.
O = 16.
In the long and manifold development of the concept of the element one idea has remained prominent from the very beginning down to our times: it is the idea of a primordial matter. Since the naive statement of Thales that all Concluding remarks. things came from water, chemists could never reconcile themselves to the fact of the conservation of the elements. By an experimental investigation which extended over five centuries and more, the impossibility of transmuting one element into another—for example, lead into gold—was demonstrated in the most extended way, and nevertheless this law has so little entered the consciousness of the chemists that it is seldom explicitly stated even in carefully written text-books. On the other side the attempts to reduce the manifoldness of the actual chemical elements to one single primordial matter have never ceased, and the latest development of science seems to endorse such a view. It is therefore necessary to consider this question from a most general standpoint.
In physical science, the chemical elements may be compared with such concepts as mass, momentum, quantity of electricity, entropy and such like. While mass and entropy are determined univocally by a unit and a number, quantity of electricity has a unit, a number and a sign, for it can be positive as well as negative. Momentum has a unit, a number and a direction in space. Elements do not have a common unit as the former magnitudes, but every element has its own unit, and there is no transition from one to another. All these magnitudes underlie a law of conservation, but to a very different degree. While mass was considered as absolutely invariable in the classical mechanics, the newer theories of the electrical constitution of matter make mass dependent on the velocity of the moving electron. Momentum also is not entirely conservative because it can be changed by light-pressure. Entropy is known as constantly increasing, remaining constant only in an ideal limiting case. With chemical elements we observe the same thing as with momentum; though till recently considered as conservative, there is now experimental evidence that they do not always show this character.
Generally the laws of the conservation of mass, weight and elements are expressed as the “law of the conservation of matter.” But this expression lacks scientific exactness because the term “matter” is generally not defined exactly, and because only the above-named properties of ponderable objects do not change, while all other properties do to a greater or less extent. Considered in the most general way, we may define matter as a complex of gravitational, kinetic and chemical energies, which are found to cling together in the same space. Of these energies the capacity factors, namely, weight, mass and elements, are conservative as described, while the intensity factors, potential, velocity and affinity, may change in wide limits. To explain why we find these energies constantly combined one with another, we only have to think of a mass without gravity or a ponderable body without mass. The first could not remain on earth because every movement would carry it into infinite space, and the second would acquire infinite velocity by the slightest push and would also disappear at once. Therefore only such objects which have both mass and weight can be handled and can be objects of our knowledge. In the same way all other energies come to our knowledge only by being (at least temporarily) associated with this combination of mass and weight. This is the true meaning of the term “matter.”
In this line of ideas matter appears not at all as a primary concept, but as a complex one; there is therefore no reason to consider matter as the last term of scientific analysis of chemical facts, and the idea of a primordial matter appears as a survival from the very first beginning of European natural philosophy. The most general concept science has developed to express the variety of experience is energy, and in terms of energy (combined with number, magnitudes, time and space) all observed and observable experiences are to be described. (W. O.)