Heroes of Science Part 4
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_"Of Heat in General._
"That this extensive subject may be treated in a profitable manner, I propose--
"First. To ascertain what I mean by the word _heat_ in these lectures.
"Secondly. To explain the meaning of the term _cold_, and ascertain the real difference between heat and cold.
"Thirdly. To mention some of the attempts which have been made to discover the nature of heat, or to form an idea of what may be the immediate cause of it.
"Fourthly and lastly. I shall begin to describe sensible effects produced by heat on the bodies to which it is communicated.
"Any person who reflects on the ideas which we annex to the word _heat_ will perceive that this word is used for two meanings, or to express two different things. It either means a sensation excited in our organs, or a certain quality, affection, or condition of the bodies around us, by which they excite in us that sensation. The word is used in the first sense when we say, we feel heat; in the second, when we say, there is heat in the fire or in a hot stone. There cannot be a sensation of heat in the fire, or in the hot stone, but the matter of the fire, or of the stone, is in a state or condition by which it excites in us the sensation of heat.
"Now, in beginning to treat of heat and its effects, I propose to use the word in this second sense only; or as expressing that state, condition, or quality of matter by which it excites in us the sensation of heat. This idea of heat will be modified a little and extended as we proceed, but the meaning of the word will continue at bottom the same, and the reason of the modification will be easily perceived."
Black's manner of dealing with the phenomenon of combustion ill.u.s.trates the clearness of the conceptions which he formed of natural phenomena, and shows moreover the thoroughly unbiased nature of his mind. As soon as he had convinced himself that the balance of evidence was in favour of the new (antiphlogistic) theory, he gave up those doctrines in which he had been trained, and accepted the teaching of the French chemists; but he did not--as some with less well-balanced minds might do--regard the new theory as a final statement, but rather as one stage nearer the complete explanation which future experiments and future reasoning would serve to establish.
In his lectures on combustion Black first of all establishes the facts, that when a body is burned it is changed into a kind (or kinds) of matter which is no longer inflammable; that the presence of air is needed for combustion to proceed; that the substance must be heated "to a certain degree" before combustion or inflammation begins; that this degree of heat (or we should now say this degree of temperature) differs for each combustible substance; that the supply of air must be renewed if the burning is to continue; and that the process of burning produces a change in the quality of the air supplied to the burning body.
He then states the phlogistic interpretation of these phenomena: that combustion is caused by the outrush from the burning body of a something called the _principle of fire_, or _phlogiston_.
Black then proceeds to demonstrate certain other facts:--When the substances produced by burning phosphorus or sulphur are heated with carbon (charcoal) the original phosphorus or sulphur is reproduced. This reproduction is due, according to the phlogistic chemists, to the giving back, by carbon, of the phlogiston which had escaped during the burning.
Hence carbon contains much phlogiston. But as a similar reproduction of phosphorus or sulphur, from the substances obtained by burning these bodies, can be accomplished by the use of substances other than carbon, it is evident that these other substances also contain much phlogiston, and, moreover, that the phlogiston contained in all these substances is one and the same _principle_. What then, he asks, is this "principle" which can so escape, and be so restored by the action of various substances? He then proceeds as follows:--
"But when we inquire further, and endeavour to learn what notion was formed of the nature of this principle, and what qualities it was supposed to have in its separate state, we find this part of the subject very obscure and unsatisfactory, and the opinions very unsettled.
"The elder chemists, and the alchemists, considered sulphur as the universal inflammable principle, or at least they chose to call the inflammable part of all bodies, that are more or less inflammable, by the name of their sulphur.... The famous German chemist Becher was, I believe, the first who rejected the notion of sulphur being the principle of inflammability in bodies.... His notion of the nature of the pure principle of inflammability was afterwards more fully explained and supported by Professor Stahl, who, agreeably to the doctrine of Becher, represented the principle of inflammability as a dry substance, or of an earthy nature, the particles of which were exquisitely subtile, and were much disposed to be agitated and set in motion with inconceivable velocity.... The opinion of Becher and Stahl concerning this _terra secunda_, or _terra inflammabilis_, or _phlogiston_, was that the atoms of it are, more than all others, disposed to be affected with an excessively swift whirling motion (_motus vorticillaris_). The particles of other elementary substances are likewise liable to be affected with the same sort of motion, but not so liable as those of _terra secunda_; and when the particles of any body are agitated with this sort of motion, the body exhibits the phenomena of heat, or ignition, or inflammation according to the violence and rapidity of the motion.... Becher and Stahl, therefore, did not suppose that heat depended on the abundance of a peculiar matter, such as the matter of heat or fire is now supposed to be, but on a peculiar motion of the particles of matter....
"This very crude opinion of the earthy nature of the principle of inflammability appears to have been deduced from a quality of many of the inflammable substances, by which they resist the action of water as a solvent. The greater number of the earthy substances are little, or not at all, soluble in water.... And when Becher and Stahl found those compounds, which they supposed contained phlogiston in the largest quant.i.ty, to be insoluble in water, although the other matter, with which the phlogiston was supposed to be united, was, in its separate state, exceedingly soluble in that fluid, they concluded that _a dry nature, or an incapability to be combined with water_, was an eminent quality of their phlogiston; and this was what they meant by calling it an earth or earthy substance.... But these authors supposed, at the same time, that the particles of this dry and earthy phlogiston were much disposed to be excessively agitated with a whirling motion; which whirling motion, exerted in all directions from the bodies in which phlogiston is contained, produced the phenomena of inflammation. This appears to have been the notion formed by Becher and Stahl, concerning the nature of the principle of inflammability, or the phlogiston; a notion which seems the least ent.i.tled to the name of explanation of anything we can think of. I presume that few persons can form any clear conception of this whirling motion, or, if they can, are able to explain to themselves how it produces, or can produce, anything like the phenomena of heat or fire."
Black then gives a clear account of the experiments of Priestley and Lavoisier (see pp. 58, 59, and 87-89), which established the presence, in common air, of a peculiar kind of gas which is especially concerned in the processes of combustion; he emphasizes the fact that a substance increases in weight when it is burned; and he gives a simple and clear statement of that explanation of combustion which is now accepted by all, and which does not require that the existence of any principle of fire should be a.s.sumed.
It is important to note that Black clearly connects the _physical_ fact that heat is absorbed, or evolved, by a substance during combustion, with the _chemical_ changes which are brought about in the properties of the substance burned. He concludes with an admirable contrast between the phlogistic theory and the theory of Lavoisier, which shows how wide, and at the same time how definite, his conceptions were. Black never speaks contemptuously of a theory which he opposes.
"According to this theory" (_i.e._ the theory of Lavoisier), "the inflammable bodies, sulphur for example, or phosphorus, are simple substances. The acid into which they are changed by inflammation is a compound. The chemists, on the contrary" (_i.e._ the followers of Stahl), "consider the inflammable bodies as compounds, and the uninflammable matter as more simple. In the common theory the heat and light are supposed to emanate from, or to be furnished by, the burning body. But, in Mr.
Lavoisier's theory, both are held to be furnished by the air, of which they are held to be const.i.tuent parts, or ingredients, while in its state of fire-supporting air."
Black was not a brilliant discoverer, but an eminently sound and at the same time imaginative worker; whatever he did he did well, but he did not exhaust any field of inquiry. Many of the facts established by him have served as the basis of important work done by those who came after him. The number of new facts added by Black to the data of chemistry was not large; but by his lectures--which are original dissertations of the highest value--he did splendid service in advancing the science of chemistry. Black possessed that which has generally distinguished great men of science, a marked honesty of character; and to this he added comprehensiveness of mental vision: he saw beyond the limits of the facts which formed the foundations of chemical science in his day. He was not a fact-collector, but a philosopher.
JOSEPH PRIESTLEY, the son of Jonas Priestley, "a maker and dresser of woollen cloth," was born at Fieldhead, near Leeds, in the year 1733. His mother, who was the daughter of a farmer near Wakefield, died when he was seven years old. From that time he was brought up by a sister of his father, who was possessed of considerable private means.
Priestley's surroundings in his young days were decidedly religious, and evidently gave a tone to his whole after life. We shall find that Priestley's work as a man of science can scarcely be separated from his theological and metaphysical work. His cast of mind was decidedly metaphysical; he was altogether different from Black, who, as we have seen, was a typical student of natural phenomena.
The house of Priestley's aunt was a resort for all the Dissenting ministers of that part of the county. She herself was strictly Calvinistic in her theological views, but not wholly illiberal.
Priestley's early schooling was chiefly devoted to learning languages; he acquired a fair knowledge of Latin, a little Greek, and somewhat later he learned the elements of Hebrew. At one time he thought of going into trade, and therefore, as he tells us in his "Memoirs," he acquired some knowledge of French, Italian and High Dutch. With the help of a friend, a Dissenting minister, he learned something of geometry, mathematics and natural philosophy, and also got some smattering of the Chaldee and Syriac tongues.
At the age of nineteen Priestley went to an "academy" at Daventry. The intellectual atmosphere here seems to have been suitable to the rapid development of Priestley's mind. Great freedom of discussion was allowed; even during the teachers' lectures the students were permitted "to ask whatever questions and to make whatever remarks" they pleased; and they did it, Priestley says, "with the greatest, but without any offensive, freedom."
The students were required to read and to give an account of the more important arguments for and against the questions discussed in the teachers' lectures. Theological disputations appear to have been the favourite topics on which the students exercised their ingenuity among themselves. Priestley tells us that he "saw reason to embrace what is generally called the heterodox side of almost every question."
Leaving this academy, Priestley went, in 1755, as a.s.sistant to the Dissenting minister at Needham, in Suffolk. Here he remained for three years, living on a salary of about 30 a year, and getting more and more into bad odour because of his peculiar theological views.
From Needham he moved to Nantwich, in Ches.h.i.+re, where he was more comfortable, and, having plenty of work to do, he had little time for abstruse speculations. School work engaged most of his time at Nantwich; he also began to collect a few scientific instruments, such as an electrical machine and an air-pump. These he taught his scholars to use and to keep in good order. He gave lectures on natural phenomena, and encouraged his scholars to make experiments and sometimes to exhibit their experiments before their parents and friends. He thus extended the reputation of his school and implanted in his scholars a love of natural knowledge.
In the year 1761 Priestley removed to Warrington, to act as tutor in a newly established academy, where he taught languages--a somewhat wide subject, as it included lectures on "The Theory of Languages," on "Oratory and Criticism," and on "The History, Laws, and Const.i.tution of England." He says, "It was my province to teach elocution, and also logic and Hebrew.
The first of these I retained, but after a year or two I exchanged the two last articles with Dr. Aikin for the civil law, and one year I gave a course of lectures on anatomy."
During his stay at Warrington, which lasted until 1767, Priestley married a daughter of Mr. Isaac Wilkinson, an ironmaster of Wrexham, in Wales. He describes his wife as "a woman of an excellent understanding much improved by reading, of great fort.i.tude and strength of mind, and of a temper in the highest degree affectionate and generous, feeling strongly for others and little for herself, also greatly excelling in everything relating to household affairs."
About this time Priestley met Dr. Franklin more than once in London. His conversation seems to have incited Priestley to a further study of natural philosophy. He began to examine electrical phenomena, and this led to his writing and publis.h.i.+ng a "History of Electricity," in the course of which he found it necessary to make new experiments. The publication of the results of these experiments brought him more into notice among scientific men, and led to his election as a Fellow of the Royal Society, and to his obtaining the degree of LL.D. from the University of Edinburgh. In the year 1767 Priestley removed to Leeds, where he spent six years as minister of Millhill Chapel.
He was able to give freer expression to his theological views in Leeds than could be done in smaller places, such as Needham and Nantwich. During this time he wrote and published many theological and metaphysical treatises.
But, what is of more importance to us, he happened to live near a brewery.
Now, the accidental circ.u.mstances, as we call them, of Priestley's life were frequently of the greatest importance in their effects on his scientific work. Black had established the existence and leading properties of fixed air about twelve or thirteen years before the time when Priestley came to live near the brewery in Leeds. He had shown that this fixed air is produced during alcoholic fermentation. Priestley knowing this used to collect the fixed air which came off from the vats in the neighbouring brewery, and amuse himself with observing its properties. But removing from this part of the town his supplies of fixed air were stopped. As however he had become interested in working with airs, he began to make fixed air for himself from chalk, and in order to collect this air he devised a very simple piece of apparatus which has played a most important part in the later development of the chemistry of gases, or pneumatic chemistry.
Priestley's _pneumatic trough_ is at this day to be found in every laboratory; it is extremely simple and extremely perfect. A dish of gla.s.s, or earthenware, or wood is partly filled with water; a shelf runs across the dish at a little distance beneath the surface of the water; a wide-mouthed bottle is filled with water and placed, mouth downwards, over a hole in this shelf. The gas which is to be collected in this bottle is generated in a suitable vessel, from which a piece of gla.s.s or metal tubing pa.s.ses under the shelf and stops just where the hole is made. The gas which comes from the apparatus bubbles up into the bottle, drives out the water, and fills the bottle. When the bottle is full of gas, it is moved to one side along the shelf, and another bottle filled with water is put in its place. As the mouth of each bottle is under water there is no connection between the gas inside and the air outside the bottle; the gas may therefore be kept in the bottle until the experimenter wants it. (See Fig.
1. which is reduced from the cut in Priestley's "Air.")
[Ill.u.s.tration: Fig. 1.]
Priestley tells us that at this time he knew very little chemistry, but he thinks that this was a good thing, else he might not have been led to make so many new discoveries as he did afterwards make.
Experimenting with fixed air, he found that water could be caused to dissolve some of the gas. In 1772 he published a pamphlet on the method of impregnating water with fixed air; this solution of fixed air in water was employed medicinally, and from this time we date the manufacture of artificial mineral waters.
The next six years of Priestley's life (1773-1779) are very important in the history of chemistry; it was during these years that much of his best work on various airs was performed. During this time he lived as a kind of literary companion (nominally as librarian) with the Earl of Shelburne (afterwards Marquis of Lansdowne.) His wife and family--he had now three children--lived at Calne, in Wilts.h.i.+re, near Lord Shelburne's seat of Bowood. Priestley spent most of the summer months with his family, and the greater part of each winter with Lord Shelburne at his London residence; during this time he also travelled in Holland and Germany, and visited Paris in 1774.
In a paper published in November 1772, Priestley says that he examined a specimen of air which he had extracted from saltpetre above a year before this date. This air "had by some means or other become noxious, but," he supposed, "had been restored to its former wholesome state, so as to effervesce with nitrous air" (in modern language, to combine with nitric oxide) "and to admit a candle to burn in it, in consequence of agitation with water." He tells us, in his "Observations on Air" (1779), that at this time he was altogether in the dark as to the nature of this air obtained from saltpetre. In August 1774, he was amusing himself by observing the action of heat on various substances--"without any particular view," he says, "except that of extracting air from a variety of substances by means of a burning lens in quicksilver, which was then a new process with me, and which I was very proud of"--when he obtained from _red precipitate_ (oxide of mercury) an air in which a candle burned with a "remarkably vigorous flame." The production of this peculiar air "surprised me more than I can well express;" "I was utterly at a loss how to account for it." At first he thought that the specimen of _red precipitate_ from which the air had been obtained was not a proper preparation, but getting fresh specimens of this salt, he found that they all yielded the same kind of air. Having satisfied himself by experiment that this peculiar air had "all the properties of common air, only in much greater perfection," he gave to it the name of _dephlogisticated air_. Later experiments taught him that the same air might be obtained from red lead, from manganese oxide, etc., by the action of heat, and from various other salts by the action of acids.
Priestley evidently regards the new "dephlogisticated air" simply as very pure ordinary air; indeed, he seems to look on all airs, or gases, as easily changeable one into the other. He always interprets his experimental results by the help of the theory of phlogiston. One would indeed think from Priestley's papers that the existence of this substance phlogiston was an unquestioned and unquestionable fact. Thus, he says in the preface to his "Experiments on Air:" "If any opinion in all the modern doctrine concerning air be well founded, it is certainly this, that nitrous air is highly charged with phlogiston, and that from this quality only it renders pure air noxious.... If I have completely ascertained anything at all relating to air it is this." Priestley thought that "very pure air" would take away phlogiston from some metals without the help of heat or any acid, and thus cause these metals to rust. He therefore placed some clean iron nails in _dephlogisticated air_ standing over mercury; after three months he noticed that about one-tenth of the air in the vessel had disappeared, and he concluded, although no rust appeared, that the dephlogisticated air had as a fact withdrawn phlogiston from the iron nails. This is the kind of reasoning which Black described to his pupils as "mere waste of time and ingenuity." The experiment with the nails was made in 1779; at this time, therefore, Priestley had no conception as to what his _dephlogisticated air_ really was.
Trying a great many experiments, and finding that the new air was obtained by the action of acids on earthy substances, Priestley was inclined to regard this air, and if this then all other airs, as made up of an acid (or acids) and an earthy substance. We now know how completely erroneous this conclusion was, but we must remember that in Priestley's time chemical substances were generally regarded as of no very definite or fixed composition; that almost any substance, it was supposed, might be changed into almost any other; that no clear meaning was attached to the word "element;" and that few, if any, careful measurements of the quant.i.ties of different kinds of matter taking part in chemical actions had yet been made.
But at the same time we cannot forget that the books of Hooke and Mayow had been published years before this time, and that twenty years before Priestley began his work on airs, Black had published his exact, scientific investigation on fixed air.
Although we may agree with Priestley that, had he made himself acquainted with what others had done before he began his own experiments, he might not have made so many new discoveries as he did, yet one cannot but think that his discoveries, although fewer, would have been more accurate.
We are told by Priestley that, when he was in Paris in 1774, he exhibited the method of obtaining dephlogisticated air from _red precipitate_ to Lavoisier and other French chemists. We shall see hereafter what important results to science followed from this visit to Lavoisier.
Let us shortly review Priestley's answer to the question, "What happens when a substance burns in air?"
Beginning to make chemical experiments when he had no knowledge of chemistry, and being an extremely rapid worker and thinker, he naturally adopted the prevalent theory, and as naturally interpreted the facts which he discovered in accordance with this theory.
When a substance burns, phlogiston, it was said, rushes out of it. But why does rapid burning only take place in air? Because, said Priestley, air has a great affinity for phlogiston, and draws it out of the burning substance.
What then becomes of this phlogiston? we next inquire. The answer is, obviously it remains in the air around the burning body, and this is proved by the fact that this air soon becomes incapable of supporting the process of burning, it becomes phlogisticated. Now, if phlogisticated air cannot support combustion, the greater the quant.i.ty of phlogiston in air, the less will it support burning; but we know that if a substance is burnt in a closed tube containing air, the air which remains when the burning is quite finished at once extinguishes a lighted candle. Priestley also proved that an air can be obtained by heating _red precipitate_, characterized by its power of supporting combustion with great vigour. What is this but common air completely deprived of phlogiston? It is dephlogisticated air. Now, if common air draws phlogiston out of substances, surely this dephlogisticated air will even more readily do the same. That it really does this Priestley thought he had proved by his experiment with clean iron nails (see p. 60).
Water was regarded as a substance which, like air, readily combined with phlogiston; but Priestley thought that a candle burned less vigorously in dephlogisticated air which had been shaken with water than in the same air before this treatment; hence he concluded that phlogiston had been taken from the water.
Heroes of Science Part 4
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