Читать книгу A History of Science - Volume 4 - Edward Huntington Williams - Страница 7

Modern chemistry may be said to have its beginning with the work of Stephen Hales (1677-1761), who early in the eighteenth century began his important study of the elasticity of air. Departing from the point of view of most of the scientists of the time, he considered air to be "a fine elastic fluid, with particles of very different nature floating in it"; and he showed that these "particles" could be separated. He pointed out, also, that various gases, or "airs," as he called them, were contained in many solid substances. The importance of his work, however, lies in the fact that his general studies were along lines leading away from the accepted doctrines of the time, and that they gave the impetus to the investigation of the properties of gases by such chemists as Black, Priestley, Cavendish, and Lavoisier, whose specific discoveries are the foundation-stones of modern chemistry.

JOSEPH BLACK

The careful studies of Hales were continued by his younger confrere, Dr. Joseph Black (1728-1799), whose experiments in the weights of gases and other chemicals were first steps in quantitative chemistry. But even more important than his discoveries of chemical properties in general was his discovery of the properties of carbonic-acid gas.

Black had been educated for the medical profession in the University of Glasgow, being a friend and pupil of the famous Dr. William Cullen. But his liking was for the chemical laboratory rather than for the practice of medicine. Within three years after completing his medical course, and when only twenty-three years of age, he made the discovery of the properties of carbonic acid, which he called by the name of "fixed air." After discovering this gas, Black made a long series of experiments, by which he was able to show how widely it was distributed throughout nature. Thus, in 1757, he discovered that the bubbles given off in the process of brewing, where there was vegetable fermentation, were composed of it. To prove this, he collected the contents of these bubbles in a bottle containing lime-water. When this bottle was shaken violently, so that the lime-water and the carbonic acid became thoroughly mixed, an insoluble white powder was precipitated from the solution, the carbonic acid having combined chemically with the lime to form the insoluble calcium carbonate, or chalk. This experiment suggested another. Fixing a piece of burning charcoal in the end of a bellows, he arranged a tube so that the gas coming from the charcoal would pass through the lime-water, and, as in the case of the bubbles from the brewer's vat, he found that the white precipitate was thrown down; in short, that carbonic acid was given off in combustion. Shortly after, Black discovered that by blowing through a glass tube inserted into lime-water, chalk was precipitated, thus proving that carbonic acid was being constantly thrown off in respiration.

The effect of Black's discoveries was revolutionary, and the attitude of mind of the chemists towards gases, or "airs," was changed from that time forward. Most of the chemists, however, attempted to harmonize the new facts with the older theories—to explain all the phenomena on the basis of the phlogiston theory, which was still dominant. But while many of Black's discoveries could not be made to harmonize with that theory, they did not directly overthrow it. It required the additional discoveries of some of Black's fellow-scientists to complete its downfall, as we shall see.

HENRY CAVENDISH

This work of Black's was followed by the equally important work of his former pupil, Henry Cavendish (1731-1810), whose discovery of the composition of many substances, notably of nitric acid and of water, was of great importance, adding another link to the important chain of evidence against the phlogiston theory. Cavendish is one of the most eccentric figures in the history of science, being widely known in his own time for his immense wealth and brilliant intellect, and also for his peculiarities and his morbid sensibility, which made him dread society, and probably did much in determining his career. Fortunately for him, and incidentally for the cause of science, he was able to pursue laboratory investigations without being obliged to mingle with his dreaded fellow-mortals, his every want being provided for by the immense fortune inherited from his father and an uncle.

When a young man, as a pupil of Dr. Black, he had become imbued with the enthusiasm of his teacher, continuing Black's investigations as to the properties of carbonic-acid gas when free and in combination. One of his first investigations was reported in 1766, when he communicated to the Royal Society his experiments for ascertaining the properties of carbonic-acid and hydrogen gas, in which he first showed the possibility of weighing permanently elastic fluids, although Torricelli had before this shown the relative weights of a column of air and a column of mercury. Other important experiments were continued by Cavendish, and in 1784 he announced his discovery of the composition of water, thus robbing it of its time-honored position as an "element." But his claim to priority in this discovery was at once disputed by his fellow-countryman James Watt and by the Frenchman Lavoisier. Lavoisier's claim was soon disallowed even by his own countrymen, but for many years a bitter controversy was carried on by the partisans of Watt and Cavendish. The two principals, however, seem never to have entered into this controversy with anything like the same ardor as some of their successors, as they remained on the best of terms.(1) It is certain, at any rate, that Cavendish announced his discovery officially before Watt claimed that the announcement had been previously made by him, "and, whether right or wrong, the honor of scientific discoveries seems to be accorded naturally to the man who first publishes a demonstration of his discovery." Englishmen very generally admit the justness of Cavendish's claim, although the French scientist Arago, after reviewing the evidence carefully in 1833, decided in favor of Watt.

It appears that something like a year before Cavendish made known his complete demonstration of the composition of water, Watt communicated to the Royal Society a suggestion that water was composed of "dephlogisticated air (oxygen) and phlogiston (hydrogen) deprived of part of its latent heat." Cavendish knew of the suggestion, but in his experiments refuted the idea that the hydrogen lost any of its latent heat. Furthermore, Watt merely suggested the possible composition without proving it, although his idea was practically correct, if we can rightly interpret the vagaries of the nomenclature then in use. But had Watt taken the steps to demonstrate his theory, the great "Water Controversy" would have been avoided. Cavendish's report of his discovery to the Royal Society covers something like forty pages of printed matter. In this he shows how, by passing an electric spark through a closed jar containing a mixture of hydrogen gas and oxygen, water is invariably formed, apparently by the union of the two gases. The experiment was first tried with hydrogen and common air, the oxygen of the air uniting with the hydrogen to form water, leaving the nitrogen of the air still to be accounted for. With pure oxygen and hydrogen, however, Cavendish found that pure water was formed, leaving slight traces of any other, substance which might not be interpreted as being Chemical impurities. There was only one possible explanation of this phenomenon—that hydrogen and oxygen, when combined, form water.

"By experiments with the globe it appeared," wrote Cavendish, "that when inflammable and common air are exploded in a proper proportion, almost all the inflammable air, and near one-fifth the common air, lose their elasticity and are condensed into dew. And by this experiment it appears that this dew is plain water, and consequently that almost all the inflammable air is turned into pure water.

"In order to examine the nature of the matter condensed on firing a mixture of dephlogisticated and inflammable air, I took a glass globe, holding 8800 grain measures, furnished with a brass cock and an apparatus for firing by electricity. This globe was well exhausted by an air-pump, and then filled with a mixture of inflammable and dephlogisticated air by shutting the cock, fastening the bent glass tube into its mouth, and letting up the end of it into a glass jar inverted into water and containing a mixture of 19,500 grain measures of dephlogisticated air, and 37,000 of inflammable air; so that, upon opening the cock, some of this mixed air rushed through the bent tube and filled the globe. The cock was then shut and the included air fired by electricity, by means of which almost all of it lost its elasticity (was condensed into water vapors). The cock was then again opened so as to let in more of the same air to supply the place of that destroyed by the explosion, which was again fired, and the operation continued till almost the whole of the mixture was let into the globe and exploded. By this means, though the globe held not more than a sixth part of the mixture, almost the whole of it was exploded therein without any fresh exhaustion of the globe."

At first this condensed matter was "acid to the taste and contained two grains of nitre," but Cavendish, suspecting that this was due to impurities, tried another experiment that proved conclusively that his opinions were correct. "I therefore made another experiment," he says, "with some more of the same air from plants in which the proportion of inflammable air was greater, so that the burnt air was almost completely phlogisticated, its standard being one-tenth. The condensed liquor was then not at all acid, but seemed pure water."

From these experiments he concludes "that when a mixture of inflammable and dephlogisticated air is exploded, in such proportions that the burnt air is not much phlogisticated, the condensed liquor contains a little acid which is always of the nitrous kind, whatever substance the dephlogisticated air is procured from; but if the proportion be such that the burnt air is almost entirely phlogisticated, the condensed liquor is not at all acid, but seems pure water, without any addition whatever."(2)

These same experiments, which were undertaken to discover the composition of water, led him to discover also the composition of nitric acid. He had observed that, in the combustion of hydrogen gas with common air, the water was slightly tinged with acid, but that this was not the case when pure oxygen gas was used. Acting upon this observation, he devised an experiment to determine the nature of this acid. He constructed an apparatus whereby an electric spark was passed through a vessel containing common air. After this process had been carried on for several weeks a small amount of liquid was formed. This liquid combined with a solution of potash to form common nitre, which "detonated with charcoal, sparkled when paper impregnated with it was burned, and gave out nitrous fumes when sulphuric acid was poured on it." In other words, the liquid was shown to be nitric acid. Now, since nothing but pure air had been used in the initial experiment, and since air is composed of nitrogen and oxygen, there seemed no room to doubt that nitric acid is a combination of nitrogen and oxygen.

This discovery of the nature of nitric acid seems to have been about the last work of importance that Cavendish did in the field of chemistry, although almost to the hour of his death he was constantly occupied with scientific observations. Even in the last moments of his life this habit asserted itself, according to Lord Brougham. "He died on March 10, 1810, after a short illness, probably the first, as well as the last, which he ever suffered. His habit of curious observation continued to the end. He was desirous of marking the progress of the disease and the gradual extinction of the vital powers. With these ends in view, that he might not be disturbed, he desired to be left alone. His servant, returning sooner than he had wished, was ordered again to leave the chamber of death, and when he came back a second time he found his master had expired."(3)

JOSEPH PRIESTLEY

While the opulent but diffident Cavendish was making his important discoveries, another Englishman, a poor country preacher named Joseph Priestley (1733-1804) was not only rivalling him, but, if anything, outstripping him in the pursuit of chemical discoveries. In 1761 this young minister was given a position as tutor in a nonconformist academy at Warrington, and here, for six years, he was able to pursue his studies in chemistry and electricity. In 1766, while on a visit to London, he met Benjamin Franklin, at whose suggestion he published his History of Electricity. From this time on he made steady progress in scientific investigations, keeping up his ecclesiastical duties at the same time. In 1780 he removed to Birmingham, having there for associates such scientists as James Watt, Boulton, and Erasmus Darwin.

Eleven years later, on the anniversary of the fall of the Bastile in Paris, a fanatical mob, knowing Priestley's sympathies with the French revolutionists, attacked his house and chapel, burning both and destroying a great number of valuable papers and scientific instruments. Priestley and his family escaped violence by flight, but his most cherished possessions were destroyed; and three years later he quitted England forever, removing to the United States, whose struggle for liberty he had championed. The last ten years of his life were spent at Northumberland, Pennsylvania, where he continued his scientific researches.

Early in his scientific career Priestley began investigations upon the "fixed air" of Dr. Black, and, oddly enough, he was stimulated to this by the same thing that had influenced Black—that is, his residence in the immediate neighborhood of a brewery. It was during the course of a series of experiments on this and other gases that he made his greatest discovery, that of oxygen, or "dephlogisticated air," as he called it. The story of this important discovery is probably best told in Priestley's own words:

"There are, I believe, very few maxims in philosophy that have laid firmer hold upon the mind than that air, meaning atmospheric air, is a simple elementary substance, indestructible and unalterable, at least as much so as water is supposed to be. In the course of my inquiries I was, however, soon satisfied that atmospheric air is not an unalterable thing; for that, according to my first hypothesis, the phlogiston with which it becomes loaded from bodies burning in it, and the animals breathing it, and various other chemical processes, so far alters and depraves it as to render it altogether unfit for inflammation, respiration, and other purposes to which it is subservient; and I had discovered that agitation in the water, the process of vegetation, and probably other natural processes, restore it to its original purity....

"Having procured a lens of twelve inches diameter and twenty inches local distance, I proceeded with the greatest alacrity, by the help of it, to discover what kind of air a great variety of substances would yield, putting them into the vessel, which I filled with quicksilver, and kept inverted in a basin of the same .... With this apparatus, after a variety of experiments.... on the 1st of August, 1774, I endeavored to extract air from mercurius calcinatus per se; and I presently found that, by means of this lens, air was expelled from it very readily. Having got about three or four times as much as the bulk of my materials, I admitted water to it, and found that it was not imbibed by it. But what surprised me more than I can express was that a candle burned in this air with a remarkably vigorous flame, very much like that enlarged flame with which a candle burns in nitrous oxide, exposed to iron or liver of sulphur; but as I had got nothing like this remarkable appearance from any kind of air besides this particular modification of vitrous air, and I knew no vitrous acid was used in the preparation of mercurius calcinatus, I was utterly at a loss to account for it."(4)

The "new air" was, of course, oxygen. Priestley at once proceeded to examine it by a long series of careful experiments, in which, as will be seen, he discovered most of the remarkable qualities of this gas. Continuing his description of these experiments, he says:

"The flame of the candle, besides being larger, burned with more splendor and heat than in that species of nitrous air; and a piece of red-hot wood sparkled in it, exactly like paper dipped in a solution of nitre, and it consumed very fast; an experiment that I had never thought of trying with dephlogisticated nitrous air.

"... I had so little suspicion of the air from the mercurius calcinatus, etc., being wholesome, that I had not even thought of applying it to the test of nitrous air; but thinking (as my reader must imagine I frequently must have done) on the candle burning in it after long agitation in water, it occurred to me at last to make the experiment; and, putting one measure of nitrous air to two measures of this air, I found not only that it was diminished, but that it was diminished quite as much as common air, and that the redness of the mixture was likewise equal to a similar mixture of nitrous and common air.... The next day I was more surprised than ever I had been before with finding that, after the above-mentioned mixture of nitrous air and the air from mercurius calcinatus had stood all night,... a candle burned in it, even better than in common air."

A little later Priestley discovered that "dephlogisticated air... is a principal element in the composition of acids, and may be extracted by means of heat from many substances which contain them.... It is likewise produced by the action of light upon green vegetables; and this seems to be the chief means employed to preserve the purity of the atmosphere."

This recognition of the important part played by oxygen in the atmosphere led Priestley to make some experiments upon mice and insects, and finally upon himself, by inhalations of the pure gas. "The feeling in my lungs," he said, "was not sensibly different from that of common air, but I fancied that my breathing felt peculiarly light and easy for some time afterwards. Who can tell but that in time this pure air may become a fashionable article in luxury?... Perhaps we may from these experiments see that though pure dephlogisticated air might be useful as a medicine, it might not be so proper for us in the usual healthy state of the body."

This suggestion as to the possible usefulness of oxygen as a medicine was prophetic. A century later the use of oxygen had become a matter of routine practice with many physicians. Even in Priestley's own time such men as Dr. John Hunter expressed their belief in its efficacy in certain conditions, as we shall see, but its value in medicine was not fully appreciated until several generations later.

Several years after discovering oxygen Priestley thus summarized its properties: "It is this ingredient in the atmospheric air that enables it to support combustion and animal life. By means of it most intense heat may be produced, and in the purest of it animals will live nearly five times as long as in an equal quantity of atmospheric air. In respiration, part of this air, passing the membranes of the lungs, unites with the blood and imparts to it its florid color, while the remainder, uniting with phlogiston exhaled from venous blood, forms mixed air. It is dephlogisticated air combined with water that enables fishes to live in it."(5)

KARL WILHELM SCHEELE

The discovery of oxygen was the last but most important blow to the tottering phlogiston theory, though Priestley himself would not admit it. But before considering the final steps in the overthrow of Stahl's famous theory and the establishment of modern chemistry, we must review the work of another great chemist, Karl Wilhelm Scheele (1742-1786), of Sweden, who discovered oxygen quite independently, although later than Priestley. In the matter of brilliant discoveries in a brief space of time Scheele probably eclipsed all his great contemporaries. He had a veritable genius for interpreting chemical reactions and discovering new substances, in this respect rivalling Priestley himself. Unlike Priestley, however, he planned all his experiments along the lines of definite theories from the beginning, the results obtained being the logical outcome of a predetermined plan.

Scheele was the son of a merchant of Stralsund, Pomerania, which then belonged to Sweden. As a boy in school he showed so little aptitude for the study of languages that he was apprenticed to an apothecary at the age of fourteen. In this work he became at once greatly interested, and, when not attending to his duties in the dispensary, he was busy day and night making experiments or studying books on chemistry. In 1775, still employed as an apothecary, he moved to Stockholm, and soon after he sent to Bergman, the leading chemist of Sweden, his first discovery—that of tartaric acid, which he had isolated from cream of tartar. This was the beginning of his career of discovery, and from that time on until his death he sent forth accounts of new discoveries almost uninterruptedly. Meanwhile he was performing the duties of an ordinary apothecary, and struggling against poverty. His treatise upon Air and Fire appeared in 1777. In this remarkable book he tells of his discovery of oxygen—"empyreal" or "fire-air," as he calls it—which he seems to have made independently and without ever having heard of the previous discovery by Priestley. In this book, also, he shows that air is composed chiefly of oxygen and nitrogen gas.

Early in his experimental career Scheele undertook the solution of the composition of black oxide of manganese, a substance that had long puzzled the chemists. He not only succeeded in this, but incidentally in the course of this series of experiments he discovered oxygen, baryta, and chlorine, the last of far greater importance, at least commercially, than the real object of his search. In speaking of the experiment in which the discovery was made he says:

"When marine (hydrochloric) acid stood over manganese in the cold it acquired a dark reddish-brown color. As manganese does not give any colorless solution without uniting with phlogiston (probably meaning hydrogen), it follows that marine acid can dissolve it without this principle. But such a solution has a blue or red color. The color is here more brown than red, the reason being that the very finest portions of the manganese, which do not sink so easily, swim in the red solution; for without these fine particles the solution is red, and red mixed with black is brown. The manganese has here attached itself so loosely to acidum salis that the water can precipitate it, and this precipitate behaves like ordinary manganese. When, now, the mixture of manganese and spiritus salis was set to digest, there arose an effervescence and smell of aqua regis."(6)

The "effervescence" he refers to was chlorine, which he proceeded to confine in a suitable vessel and examine more fully. He described it as having a "quite characteristically suffocating smell," which was very offensive. He very soon noted the decolorizing or bleaching effects of this now product, finding that it decolorized flowers, vegetables, and many other substances.

Commercially this discovery of chlorine was of enormous importance and the practical application of this new chemical in bleaching cloth soon supplanted the old process of crofting—that is, bleaching by spreading the cloth upon the grass. But although Scheele first pointed out the bleaching quality of his newly discovered gas, it was the French savant, Berthollet, who, acting upon Scheele's discovery that the new gas would decolorize vegetables and flowers, was led to suspect that this property might be turned to account in destroying the color of cloth. In 1785 he read a paper before the Academy of Sciences of Paris, in which he showed that bleaching by chlorine was entirely satisfactory, the color but not the substance of the cloth being affected. He had experimented previously and found that the chlorine gas was soluble in water and could thus be made practically available for bleaching purposes. In 1786 James Watt examined specimens of the bleached cloth made by Berthollet, and upon his return to England first instituted the process of practical bleaching. His process, however, was not entirely satisfactory, and, after undergoing various modifications and improvements, it was finally made thoroughly practicable by Mr. Tennant, who hit upon a compound of chlorine and lime—the chloride of lime—which was a comparatively cheap chemical product, and answered the purpose better even than chlorine itself.

To appreciate how momentous this discovery was to cloth manufacturers, it should be remembered that the old process of bleaching consumed an entire summer for the whitening of a single piece of linen; the new process reduced the period to a few hours. To be sure, lime had been used with fair success previous to Tennant's discovery, but successful and practical bleaching by a solution of chloride of lime was first made possible by him and through Scheele's discovery of chlorine.

Until the time of Scheele the great subject of organic chemistry had remained practically unexplored, but under the touch of his marvellous inventive genius new methods of isolating and studying animal and vegetable products were introduced, and a large number of acids and other organic compounds prepared that had been hitherto unknown. His explanations of chemical phenomena were based on the phlogiston theory, in which, like Priestley, he always, believed. Although in error in this respect, he was, nevertheless, able to make his discoveries with extremely accurate interpretations. A brief epitome of the list of some of his more important discoveries conveys some idea, of his fertility of mind as well as his industry. In 1780 he discovered lactic acid,(7) and showed that it was the substance that caused the acidity of sour milk; and in the same year he discovered mucic acid. Next followed the discovery of tungstic acid, and in 1783 he added to his list of useful discoveries that of glycerine. Then in rapid succession came his announcements of the new vegetable products citric, malic, oxalic, and gallic acids. Scheele not only made the discoveries, but told the world how he had made them—how any chemist might have made them if he chose—for he never considered that he had really discovered any substance until he had made it, decomposed it, and made it again.