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a history of science-4-第2部分

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another in many respects; were alike in combustibility。 From this he argued that all combustible substances must contain a common principle; and this principle he named phlogiston。 This phlogiston he believed to be intimately associated in combination with other substances in nature; and in that condition not perceivable by the senses; but it was supposed to escape as a substance burned; and become apparent to the senses as fire or flame。 In other words; phlogiston was something imprisoned in a combustible structure (itself forming part of the structure); and only liberated when this structure was destroyed。 Fire; or flame; was FREE phlogiston; while the imprisoned phlogiston was called COMBINED PHLOGISTON; or combined fire。 The peculiar quality of this strange substance was that it disliked freedom and was always striving to conceal itself in some combustible substance。  Boyle's tentative suggestion that heat was simply motion was apparently not accepted by Stahl; or perhaps it was unknown to him。

According to the phlogistic theory; the part remaining after a substance was burned was simply the original substance deprived of phlogiston。 To restore the original combustible substance; it was necessary to heat the residue of the combustion with something that burned easily; so that the freed phlogiston might again combine with the ashes。 This was explained by the supposition that the more combustible a substance was the more phlogiston it contained; and since free phlogiston sought always to combine with some suitable substance; it was only necessary to mix the phlogisticating agents; such as charcoal; phosphorus; oils; fats; etc。; with the ashes of the original substance; and heat the mixture; the phlogiston thus freed uniting at once with the ashes。  This theory fitted very nicely as applied to the calcined lead revivified by the grains of wheat; although with some other products of calcination it did not seem to apply at all。

It will be seen from this that the phlogistic theory was a step towards chemistry and away from alchemy。  It led away from the idea of a 〃spirit〃 in metals that could not be seen; felt; or appreciated by any of the senses; and substituted for it a principle which; although a falsely conceived one; was still much more tangible than the 〃spirit;〃 since it could be seen and felt as free phlogiston and weighed and measured as combined phlogiston。 The definiteness of the statement that a metal; for example; was composed of phlogiston and an element was much less enigmatic; even if wrong; than the statement of the alchemist that 〃metals are produced by the spiritual action of the three principles; salt; mercury; sulphur〃particularly when it is explained that salt; mercury; and sulphur were really not what their names implied; and that there was no universally accepted belief as to what they really were。

The metals; which are now regarded as elementary bodies; were considered compounds by the phlogistians; and they believed that the calcining of a metal was a process of simplification。 They noted; however; that the remains of calcination weighed more than the original product; and the natural inference from this would be that the metal must have taken in some substance rather than have given off anything。  But the phlogistians had not learned the all…important significance of weights; and their explanation of variation in weight was either that such gain or loss was an unimportant 〃accident〃 at best; or that phlogiston; being light; tended to lighten any substance containing it; so that driving it out of the metal by calcination naturally left the residue heavier。

At first the phlogiston theory seemed to explain in an indisputable way all the known chemical phenomena。  Gradually; however; as experiments multiplied; it became evident that the plain theory as stated by Stahl and his followers failed to explain satisfactorily certain laboratory reactions。  To meet these new conditions; certain modifications were introduced from time to time; giving the theory a flexibility that would allow it to cover all cases。 But as the number of inexplicable experiments continued to increase; and new modifications to the theory became necessary; it was found that some of these modifications were directly contradictory to others; and thus the simple theory became too cumbersome from the number of its modifications。 Its supporters disagreed among themselves; first as to the explanation of certain phenomena that did not seem to accord with the phlogistic theory; and a little later as to the theory itself。  But as yet there was no satisfactory substitute for this theory; which; even if unsatisfactory; seemed better than anything that had gone before or could be suggested。

But the good effects of the era of experimental research; to which the theory of Stahl had given such an impetus; were showing in the attitude of the experimenters。 The works of some of the older writers; such as Boyle and Hooke; were again sought out in their dusty corners and consulted; and their surmises as to the possible mixture of various gases in the air were more carefully considered。  Still the phlogiston theory was firmly grounded in the minds of the philosophers; who can hardly be censured for adhering to it; at least until some satisfactory substitute was offered。  The foundation for such a theory was finally laid; as we shall see presently; by the work of Black; Priestley; Cavendish; and Lavoisier; in the eighteenth century; but the phlogiston theory cannot be said to have finally succumbed until the opening years of the nineteenth century。



II。 THE BEGINNINGS OF MODERN CHEMISTRY

THE 〃PNEUMATIC〃 CHEMISTS

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; be 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; be 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 theoriesto 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 f
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