Part 51

Introduction.

As we look back to the time of the founding of the Journal in 1818, we see that the science of chemistry had recently made and was then making great advances. That the scientific men of those days were much impressed with what was being accomplished is well shown by the following statement made in an early number of the Journal (=3=, 330, 1821) by its founder in reviewing Gorham’s Elements of Chemical Science. He says: “The present period is distinguished by wonderful mental activity; it might indeed be denominated as the intellectual age of the world. At no former period has the mind of man been directed at one time to so many and so useful researches.”

A very remarkable revolution in chemical ideas had recently taken place. Soon after the discovery of oxygen by Priestley in 1774, and the subsequent discovery by Cavendish that water was formed by the combustion of hydrogen and oxygen, Lavoisier had explained combustion in general as oxidation, thus overthrowing the curious old phlogiston theory which had prevailed as the basis of chemical philosophy for nearly a century.

The era of modern chemistry had thus begun, and the additional views that matter was indestructible and that chemical compounds were of constant composition had been generally accepted at the beginning of the nineteenth century.

Dalton had announced his atomic theory in 1802, having based it largely upon the law of multiple proportions which he had previously discovered, and he had begun to express the formulas for compounds in terms of atomic symbols.

In 1808 Gay-Lussac had discovered his law of gas combination in simple proportions, a law of supreme importance in connection with the atomic theory, but neither he nor Dalton had seen this theoretical connection. Avogadro had understood it, however, and in 1811 had reached the momentous conclusion that all gases and vapors have equal numbers of molecules in equal volumes at the same temperature and pressure.

Davy in 1807 had isolated the alkali-metals, sodium and potassium, by means of electrolysis, thus practically dispelling the view that certain earthy substances might be elementary; and about four years later he had demonstrated that chlorine was an element, not an oxide as had been supposed previously, thus overthrowing Lavoisier’s view that oxygen was the characteristic constituent of all acids.

At the time that our period of history begins, the atomic theory had been accepted generally, but in a somewhat indefinite form, since little attention had been paid to Avogadro’s principle, and since Dalton had used only the principle of greatest simplicity in writing the formulas of compounds, considering water as HO and ammonia NH, for example. At this time, however, Berzelius for ten or fifteen years had been devoting tremendous energy to the task of determining the atomic weights of nearly all of the elements then known by analyzing their compounds. He had confirmed the law of multiple proportions, accepted the atomic theory, and utilized Avogadro’s principle, and it is an interesting coincidence that his first table of atomic weights was published in the year 1818.

An interesting account of the views on chemistry held at about that time was published in the Journal by Denison Olmsted (=11=, 349, 1826; =12=, 1, 1827), who had recently become professor of natural philosophy in Yale College.

The most illustrious European chemists of that time were Berzelius of Sweden, Davy of England, and Gay-Lussac of France, and the curious circumstance may be mentioned that all three of them and also Benjamin Silliman, the founder of the Journal, were born within a period of eight months in 1778–1779.

In this country Robert Hare of Philadelphia and Benjamin Silliman were undoubtedly the most prominent chemists of those days. Hare is best known for his invention of the compound blowpipe, but his contributions to the Journal were very numerous, beginning almost with the first volume and continuing for over thirty years. Among the first of these contributions was a most vigorous but well-merited attack upon a Doctor Clark of Cambridge, England, who had copied his invention without giving him proper credit. He begins (=2=, 281, 1820) by saying: “Dr. Clark has published a book on the gas blowpipe in which he professes a sincere desire to render everyone his due. That it would be difficult for the conduct of any author to be more discordant with these professions, I pledge myself to prove in the following pages.”

Hare also invented a galvanic battery which he called a “deflagrator,” consisting of a large number of single cells in series. With this, using carbon electrodes, he was able to obtain a higher temperature than with his oxy-hydrogen blowpipe. He was the first to apply galvanic ignition to blasting (=21=, 139, 1832), and he first carried out electrolyses with the use of mercury as the cathode (=37=, 267, 1839). In this way he prepared metallic calcium and other metals from solutions of their chlorides, while the principle employed by him has in recent times been used as the basis of a very important process for manufacturing caustic potash and soda.

Silliman, who had become an intimate friend of Hare during two periods of chemical study under Woodhouse in Philadelphia in 1802–1804, and who soon afterwards spent fourteen months as a student abroad, chiefly in England and Scotland, took a broad interest in science and gave much attention to geology as well as to chemistry. In spite of this divided interest and his work as a teacher, popular scientific lecturer, and editor, he found time for a surprising amount of original chemical work. For instance, using Hare’s deflagrator, he showed that carbon was volatilized in the electric arc (=5=, 108, 1822); he was the first in this country to prepare hydrofluoric acid (=6=, 354, 1823), and he first detected bromine in one of our natural brines (=18=, 142, 1830).

Atomic Weights.

As soon as the atomic theory was accepted, the relative weights of the atoms became a matter of vital importance in connection with formulas and chemical calculations. In advancing his theory, Dalton had made some very rough atomic weight determinations, and it has been mentioned already that Berzelius, at the time that our historical period begins, was engaged in the prodigious task of accurately determining these constants for nearly all the known elements. It is recorded that he analyzed quantitatively no less than two thousand compounds in connection with this work during his career. His table of 1818 has proved to be remarkably accurate for that pioneer period, and it indicates his remarkable skill as an analyst.

It is to be observed that Berzelius in this early table made use of Avogadro’s principle in connection with elements forming gaseous compounds, and thus obtained correct formulas and atomic weights in such cases, but that in many instances his atomic weights and those now accepted bear the relation of simple multiples to one another, because he had then no means of deciding upon the formulas of many compounds except the rule of assumed simplicity. For example, the two oxides of iron now considered to be FeO and Fe{2}O{3} he regarded as FeO{2} and FeO{3}, knowing as he did that the ratio of oxygen in them was 2 to 3, and believing that a single atom of iron in each was the simplest view of the case, so that as the consequence of these formulas the atomic weight of iron was then considered to be practically twice as great in its relation to oxygen as at present.

These old atomic weights of Berzelius, used with the corresponding formulas, were just as serviceable for calculating compositions and analytical factors as though the correct multiples had been selected. As time went on, the true multiples were gradually found from considerations of atomic heats, isomorphism, vapor densities, the periodic law, and so on, and suitable changes were made in the chemical formulas.

Berzelius used 100 parts of oxygen as the basis of his atomic weights, a practice which was generally followed for several decades. Dalton, however, had originally used hydrogen as unity as the basis, and this plan finally came into use everywhere, as it seemed to be more logical and convenient, because hydrogen has the smallest atomic weight, and also because the atomic weights of a number of common elements appeared to be exact multiples of that of hydrogen, thus giving simpler numbers for use in calculations.

Within a few years a slight change has been made by the adoption of oxygen as exactly 16 as the basis, which gives hydrogen the value of 1·008.

As early as 1815, Prout, an English physician, had advanced the view that hydrogen is the primordial substance of all the elements, and consequently that the atomic weights are all exact multiples of that of hydrogen. This hypothesis has been one of the incentives to investigations upon atomic weights, for it has been found that these constants in the cases of a considerable number of the elements are very close to whole numbers when based upon hydrogen as unity, or even still closer when based upon oxygen as 16.

With our present knowledge Prout’s hypothesis may be regarded as disproved for nearly all the elements whose atomic weights have been accurately determined, but the close or even exact agreement with it in a few cases is still worthy of consideration. There is an interesting letter from Berzelius to B. Silliman, Jr., in the Journal (=48=, 369, 1845) in which Berzelius considers the theory entirely disproved.

For a long time entire reliance was placed upon the atomic weights obtained by Berzelius, but it came to be observed that the calculation of carbon from carbon dioxide appeared to give high results in certain cases, so that doubt arose as to the accuracy of Berzelius’s work. Consequently in 1840 Dumas, assisted by his pupil Stas, made a new determination of the atomic weight of carbon, and found that the number obtained by Berzelius, 12·12, was slightly too large. Subsequently Dumas determined more than twenty other atomic weights, but this great amount of work did not bring about any considerable improvement, for it appears that Dumas did not greatly excel Berzelius in accuracy, and that the latter had made one of his most noticeable errors in connection with carbon.

Soon after assisting Dumas in the work upon carbon, Stas began his very extensive and accurate, independent determinations, leading to the publication of a book in 1867 describing his work. Stas made many improvements in methods by the use of great care in purifying the substances employed, and especially by using large quantities of material in his determinations, thus diminishing the proportional errors in weighing. His results, which dealt with most of the common elements, were accepted with much confidence by chemists everywhere.

Stas reached the conclusion that there could be no real foundation for Prout’s hypothesis, since so many of his atomic weights varied from whole numbers, and this opinion has been generally accepted.

The first accurate atomic weight determination published in the Journal was that by Mallett on lithium (=22=, 349, 1856; =28=, 349, 1859), showing a result almost identical with that accepted at the present time. Johnson and Allen’s determination (=35=, 94, 1863) on the rare element cæsium was carried out with extraordinary accuracy. Lee, working with Wolcott Gibbs, made good determinations on nickel and cobalt (=2=, 44, 1871). The work of Cooke on antimony (=15=, 41, 107, 1878) was excellent.

Concerning the more recent work published elsewhere than in the Journal, attention should be called particularly to the investigations that have been carried on for the past twenty-five years by Richards and his associates at Harvard University. Richards has shown masterly ability in the selection of methods and in avoiding errors. His results have displayed such marvelous agreements among repeated determinations by the same and by different processes as to inspire the greatest confidence. His work has been very extensive, and it is a great credit to our country that this atomic weight work, so superior to all that has been previously done, is being carried out here.

It may be mentioned that for a number of years the decision in regard to the atomic weights to be accepted has been in the hands of an International Committee of which our fellow countryman F. W. Clarke has been chairman. In connection with this position and previously, Clarke has done valuable service in re-calculating and summarizing atomic weight determinations.

Analytical Chemistry.