Heroes of Science: Chemists

One of the most commonly occurring and most noticeable changes in the properties of matter is that which proceeds when a piece of wood, or a candle, or a quantity of oil burns. The solid wood, or candle, or the liquid oil slowly disappears, and this disappearance is attended with the visible formation of flame. Even the heavy fixed metals, tin or lead, may be caused to burn; light is produced, a part of the metal seems to disappear, and a white (or reddish) solid, very different from the original metal, remains. The process of burning presents all those peculiarities which are fitted to strike an observer of the changes of Nature; that is, which are fitted to strike a chemist—for chemistry has always been recognized as having for its object to explain the changes which matter undergoes. The chemists of the seventeenth and eighteenth centuries were chiefly occupied in trying to explain this process of burning or combustion.

Van Helmont (1577-1644), who was a physician and chemist of Brussels, clearly distinguished between common air and other "airs" or gases produced in different ways. Robert Hooke (1635-1703), one of the original Fellows of the Royal Society, in the "Micographia, or Philosophical Description of Minute Bodies," published in 1665, concluded from the results of numerous experiments that there exists in common air a peculiar kind of gas, similar to, or perhaps identical with the gas or air which is got by heating saltpetre; and he further supposed that when a solid burns, it is dissolved by (or we should now say, it is converted into a gas by combining with) this peculiar constituent of the air.

John Mayow (1645-1679), a physician of Oxford, experimented on the basis of facts established by Hooke. He showed that when a substance, e.g. a candle, burns in air, the volume of air is thereby lessened. To that portion of the air which had dissolved the burned substance he gave the name of nitre-air, and he argued that this air exists in condensed form in nitre, because sulphur burns when heated with nitre in absence of common air. Mayow added the most important fact—a fact which was forgotten by many later experimenters—that the solid substance obtained by burning a metal in air weighs more than the metal itself did before burning. He explained this increase in weight by saying that the burning metal absorbs particles of "nitre-air" from the atmosphere. Thus Hooke and Mayow had really established the fact that common air consists of more than one definite kind of matter—in other words, that common air is not an element; but until recent times the term "element" or "elementary principle" was used without any definite meaning. When we say that the ancients and the alchemists recognized four elements—earth, air, fire, and water—we do not attach to the word "element" the same definite meaning as when we now say, "Iron is an element."

From earth, air, fire and water other substances were obtained; or it might be possible to resolve other substances into one or more of these four. But even to such a word as "substance" or "matter" no very definite meaning could be attached. Although, therefore, the facts set forth by Hooke and Mayow might now justify the assertion that air is not an element, they did not, in the year 1670, necessarily convey this meaning to men's minds. The distinction between element and compound was much more clearly laid down by the Hon. Robert Boyle (1627-1691), whose chemical work was wonderfully accurate and thorough, and whose writings are characterized by acute scientific reasoning. We shall again return to these terms "element" and "compound."

But the visible and striking phenomenon in most processes of burning is the production of light and sometimes of flame. The importance of the fact that the burned substance (when a solid) weighs more than the unburned substance was overshadowed by the apparent importance of the outward part of the process, which could scarcely be passed over by any observer. There appears to be an outrush of something from the burning substance. There is an outrush of something, said Becher and Stahl, and this something is the "principle of fire." The principle of fire, they said, is of a very subtle nature; its particles, which are always in very rapid motion, can penetrate any substance, however dense. When metals burn—the argument continued—they lose this principle of fire; when the burned metal—or calx as it was usually called—is heated with charcoal it regains this "principle," and so the metal is re-formed from the calx.

Thus arose the famous theory of phlogiston (from Greek, = "burned"), which served as a central nucleus round which all chemical facts were grouped for nearly a hundred years.

John Joachim Becher was born at Speyer in 1635, and died in 1682; in his chemical works, the most important of which is the "Physica Subterranea," he retained the alchemical notion that the metals are composed of three "principles"—the nitrifiable, the combustible, and the mercurial—and taught that during calcination the combustible and mercurial principles are expelled, while the nitrifiable remains in the calx.

George Ernest Stahl—born at Anspach in 1660, and died at Berlin in 1734—had regard chiefly to the principles which escape during the calcination of metals, and simplifying, and at the same rendering more definite the idea of Becher, he conceived and enunciated the theory of phlogiston.

But if something (name it "phlogiston" or call it by any other name you please) is lost by a metal when the metal is burned, how is it that the loss of this thing is attended with an increase in the weight of the matter which loses it? Either the theory of phlogiston must be abandoned, or the properties of the thing called phlogiston must be very different from those of any known kind of matter.

Stahl replied, phlogiston is a "principle of levity;" the presence of phlogiston in a substance causes that substance to weigh less than it did before it received this phlogiston.

In criticizing this strange statement, we must remember that in the middle of the seventeenth century philosophers in general were not firmly convinced of the truth that the essential character of matter is that it possesses weight, nor of the truth that it is impossible to destroy or to create any quantity of matter however small. It was not until the experimental work of Lavoisier became generally known that chemists were convinced of these truths. Nevertheless, the opponents of the Stahlian doctrine were justified in asking for further explanations—in demanding that some other facts analogous to this supposed fact, viz. that a substance can weigh less than nothing, should be experimentally established.

The phlogistic theory however maintained its ground; we shall find that it had a distinct element of truth in it, but we shall also find that it did harm to scientific advance. This theory was a wide and sweeping generalization from a few facts; it certainly gave a central idea around which some facts might be grouped, and it was not very difficult, by slightly cutting down here and slightly adding there, to bring many new discoveries within the general theory.

We now know that in order to explain the process of combustion much more accurate knowledge was required than the chemists of the seventeenth century possessed; but we ought to be thankful to these chemists, and notably to Stahl, that they did not hesitate to found a generalization on the knowledge they had. Almost everything propounded in natural science has been modified as man's knowledge of nature has become wider and more accurate; but it is because the scientific student of nature uses the generalizations of to-day as stepping-stones to the better theories of to-morrow, that science grows "from more to more."

Looking at the state of chemistry about the middle of the eighteenth century, we find that the experiments, and especially the measurements, of Hooke and Mayow had laid a firm basis of fact concerning the process of combustion, but that the phlogistic theory, which appeared to contradict these facts, was supreme; that the existence of airs, or gases, different from common air was established, but that the properties of these airs were very slightly and very inaccurately known; that Boyle had distinguished element from compound and had given definite meanings to these terms, but that nevertheless the older and vaguer expression, "elementary principle," was generally used; and lastly, that very few measurements of the masses of the different kinds of matter taking part in chemical changes had yet been made.

CHAPTER II.

ESTABLISHMENT OF CHEMISTRY AS A SCIENCE —PERIOD OF BLACK, PRIESTLEY AND LAVOISIER.

Joseph Black, 1728-1799. Joseph, Priestley, 1733-1804. Antoine Laurent Lavoisier, 1743-1794.

During this period of advance, which may be broadly stated as comprising the last half of the eighteenth century, the aim and scope of chemical science were clearly indicated by the labours of Black, Priestley and Lavoisier. The work of these men dealt chiefly with the process of combustion. Black and Priestley finally proved the existence of airs or gases different from common air, and Lavoisier applied these discoveries to give a clear explanation of what happens when a substance burns.

Joseph Black was born near Bordeaux in the year 1728. His father was of Scottish family, but a native of Belfast; his mother was the daughter of Mr. Gordon, of Hilhead in Aberdeenshire. We are told by Dr. Robison, in his preface to Black's Lectures, that John Black, the father of Joseph, was a man "of most amiable manners, candid and liberal in his sentiments, and of no common information."

At the age of twelve Black was sent home to a school at Belfast; after spending six years there he went to the University of Glasgow in the year 1746. Little is known of his progress at school or at the university, but judging from his father's letters, which his son preserved, he seems to have devoted himself to study. While at Glasgow he was attracted to the pursuit of physical science, and chose medicine as a profession. Becoming a pupil of Dr. Cullen, he was much impressed with the importance of chemical knowledge to the student of medicine. Dr. Cullen appears to have been one of the first to take large and philosophical views of the scope of chemical science, and to attempt to raise chemistry from the rank of a useful art to that of a branch of natural philosophy. Such a man must have been attracted by the young student, whose work was already at once accurate in detail and wide in general scope.

In the notes of work kept by Black at this time are displayed those qualities of methodical arrangement, perseverance and thoroughness which are so prominent in his published investigations and lectures. In one place we find, says his biographer, many disjointed facts and records of diverse observations, but the next time he refers to the same subjects we generally have analogous facts noted and some conclusions drawn—we have the beginnings of knowledge. Having once entered on an investigation Black works it out steadily until he gets definite results.

His earlier notes are concerned chiefly with heat and cold; about 1752 he begins to make references to the subject of "fixed air."

About 1750 Black went to Edinburgh University to complete his medical studies, and here he was again fortunate in finding a really scientific student occupying the chair of natural philosophy.

The attention of medical men was directed at this time to the action of limewater as a remedy for stone in the bladder. All the medicines which were of any avail in mitigating the pain attendant on this disease more or less resembled the "caustic ley of the soap-boilers" (or as we should now call it caustic potash or soda). These caustic medicines were mostly prepared by the action of quicklime on some other substance, and quicklime was generally supposed to derive its caustic, or corrosive properties from the fire which was used in changing ordinary limestone into quicklime.

When quicklime was heated with "fixed alkalis" (i.e. with potassium or sodium carbonate), it changed these substances into caustic bodies which had a corrosive action on animal matter; hence it was concluded that the quicklime had derived a "power"—or some said had derived "igneous matter"—from the fire, and had communicated this to the fixed alkalis, which thereby acquired the property of corroding animal matter.

Black thought that he might be able to lay hold of this "igneous matter" supposed to be taken by the limestone from the fire; but he found that limestone loses weight when changed into quicklime. He then dissolved limestone (or chalk) in spirits of salt (hydrochloric acid), and compared the loss of weight undergone by the chalk in this process with the loss suffered by an equal quantity of chalk when strongly heated. This investigation led Black to a fuller study of the action of heat on chalk and on "mild magnesia" (or as we now say, magnesium carbonate).

In order that his experiments might be complete and his conclusions well established, he delayed taking the degree of Doctor of Medicine for three years. He graduated as M. D. in 1755, and presented his thesis on "Magnesia Alba, Quicklime and other Alkaline Substances," which contained the results of what is probably the first accurately quantitative examination of a chemical action which we possess.

Black prepared mild magnesia (magnesium carbonate) by boiling together solutions of Epsom salts (magnesium sulphate) and fixed alkali (potassium carbonate). He showed that when mild magnesia is heated—

1. It is much decreased in bulk.

2. It loses weight (twelve parts become five, according to Black).

3. It does not precipitate lime from solutions of that substance in acids (Black had already shown that mild magnesia does precipitate lime).

He then strongly heated a weighed quantity of mild magnesia in a retort connected with a receiver; a few drops of water were obtained in the receiver, but the magnesia lost six or seven times as much weight as the weight of the water produced. Black then recalls the experiments of Hales, wherein airs other than common air had been prepared, and concludes that the loss of weight noticed when mild magnesia is calcined is probably due to expulsion, by the heat, of some kind of air. Dissolving some of his mild magnesia in acid he noticed that effervescence occurred, and from this he concluded that the same air which, according to his hypothesis, is expelled by heat, is also driven out from the mild magnesia by the action of acid. He then proceeded to test this hypothesis. One hundred and twenty grains of mild magnesia were strongly calcined; the calcined matter, amounting to seventy grains, was dissolved in dilute oil of vitriol, and this solution was mixed with common fixed alkali (potassium carbonate). The solid which was thus produced was collected, washed and weighed; it amounted to a trifle less than one hundred and twenty grains, and possessed all the properties—detailed by Black—of the original mild magnesia. But this is exactly the result which ought to have occurred according to his hypothesis.

The next step in the investigation was to collect the peculiar air which Black had proved to be evolved during the calcination of mild magnesia. To this substance he gave the name of "fixed air," because it was fixed or held by magnesia. Black established the existence of this air in the expired breath of animals, and also showed that it was present in the air evolved during vinous fermentation. He demonstrated several of its properties; among these, the fact that animals die when placed in this air. An air with similar properties was obtained by calcining chalk. Black held that the chemical changes which occur when chalk is calcined are exactly analogous to those which he had proved to take place when magnesia is strongly heated. Chalk ought therefore to lose weight when calcined; the residue ought to neutralize an acid without evolution of any gas, and the quantity of acid thus neutralized ought to be the same as would be neutralized by the uncalcined chalk; lastly, it ought to be possible to recover the uncalcined chalk by adding a fixed alkali to a solution of the calcined chalk or quicklime.

The actual results which Black obtained were as follows:—

One hundred and twenty grains of chalk were dissolved in dilute muriatic (hydrochloric) acid; 421 grains of the acid were needed to neutralize the chalk, and 48 grains of fixed air were evolved. One hundred and twenty grains of the same specimen of chalk were strongly calcined, and then dissolved in dilute muriatic acid; 414 grains of the acid were required to neutralize the calcined chalk. The difference between 421 and 414 is very slight; considering the state of practical chemistry at Black's time, we may well agree with him that he was justified in the conclusion that equal weights of calcined and of uncalcined chalk neutralize the same amount of acid. One hundred and twenty grains of the same specimen of chalk were again strongly heated; the calcined chalk, amounting to 68 grains, was digested with a solution of fixed alkali in water. The substance thus obtained, when washed and dried, weighed 118 grains, and had all the properties of ordinary chalk. Therefore, said Black, it is possible to recover the whole of the chalk originally present before calcination, by adding a fixed alkali to the calcined chalk or quicklime.

At this time it was known that water dissolves quicklime, but it was generally held that only about one-fourth (or perhaps a little more) of any specimen of quicklime could be dissolved by water, however much water was employed. Black's researches had led him to regard quicklime as a homogeneous chemical compound; he concluded that as water undoubtedly dissolves quicklime to some extent, any specimen of this substance, provided it be pure, must be wholly soluble in water. Carefully conducted experiments proved that Black's conclusion was correct. Black had thus proved that quicklime is a definite substance, with certain fixed properties which characterize it and mark it off from all other substances; that by absorbing, or combining with another definite substance (fixed air), quicklime is changed into a third substance, namely chalk, which is also characterized by properties as definite and marked as those of quicklime or fixed air.

Black, quite as much as the alchemists, recognized the fact that change is continually proceeding in Nature; but he clearly established the all-important conclusion that these natural changes proceed in definite order, and that it is possible by careful experiment and just reasoning to acquire a knowledge of this order. He began the great work of showing that, as in other branches of natural science, so also in chemistry, which is pre-eminently the study of the changes of Nature, "the only distinct meaning of that word" (natural) "is stated, fixed, or settled" (Butler's "Analogy," published 1736).

This research by Black is a model of what scientific work ought to be. He begins with a few observations of some natural phenomenon; these he supplements by careful experiments, and thus establishes a sure basis of fact; he then builds on this basis a general hypothesis, which he proceeds to test by deducing from it certain necessary conclusions, and proving, or disproving, these by an appeal to Nature. This is the scientific method; it is common sense made accurate.

Very shortly after the publication of the thesis on magnesia and quicklime, a vacancy occurred in the chemical chair in Glasgow University, and Black was appointed Professor of Anatomy and Lecturer on Chemistry. As he did not feel fully qualified to lecture on anatomy, he made an arrangement to exchange subjects with the Professor of Medicine, and from this time he delivered lectures on chemistry and on "The Institutes of Medicine."

Black devoted a great deal of care and time to the teaching duties of his chair. His chemical experimental researches were not much advanced after this time; but he delivered courses of lectures in which new light was thrown on the whole range of chemical science.

In the years between 1759 and 1763 Black examined the phenomena of heat and cold, and gave an explanation, founded on accurate experiments, of the thermal changes which accompany the melting of solids and the vaporization of liquids.

If pieces of wood, lead and ice be taken by the hand from a box in which they have been kept cold, the wood feels cold to the touch, the lead feels colder than the wood, and the ice feels colder than the lead; hence it was concluded that the hand receives cold from the wood, more cold from the lead, and most cold from the ice.

Black however showed that the wood really takes away heat from the hand, but that as the wood soon gets warmed, the process stops before long; that the lead, not being so quickly warmed as the wood, takes away more heat from the hand than the wood does, and that the ice takes away more heat than either wood or lead.

Black thought that the heat which is taken by melting ice from a warm body remains in the water which is produced; as soon as winter came he proceeded to test this supposition by comparing the times required to melt one pound of ice and to raise the temperature of one pound of water through one degree, the source of heat being the same in each case. He also compared the time required to lower the temperature of one pound of water through one degree with that required to freeze one pound of ice-cold water. He found that in order to melt one pound of ice without raising its temperature, as much heat had to be added to the ice as sufficed to raise the temperature of one pound of water through about 140 degrees of Fahrenheit's thermometer. But this heat which has been added to the ice to convert it into water is not indicated by the thermometer. Black called this "latent heat."

The experimental data and the complete theory of latent heat were contained in a paper read by Black to a private society which met in the University of Glasgow, on April 23, 1762; but it appears that Black was accustomed to teach the theory in his ordinary lectures before this date.

The theory of latent heat ought also to explain the phenomena noticed when liquid water is changed into steam. Black applied his theory generally to this change, but did not fully work out the details and actually measure the quantity of heat which is absorbed by water at the boiling point before it is wholly converted into steam at the same temperature, until some years later when he had the assistance of his pupil and friend James Watt.

Taking a survey of the phenomena of Nature, Black insisted on the importance of these experimentally established facts—that before ice melts it must absorb a large quantity of heat, and before water is vaporized it must absorb another large quantity of heat, which amounts of heat are restored to surrounding substances when water vapour again becomes liquid water and when liquid water is congealed to ice. He allows his imagination to picture the effects of these properties of water in modifying and ameliorating the climates of tropical and of Northern countries. In his lectures he says, "Here we can also trace another magnificent train of changes which are nicely accommodated to the wants of the inhabitants of this globe. In the equatorial regions, the oppressive heat of the sun is prevented from a destructive accumulation by copious evaporation. The waters, stored with their vaporific heat, are then carried aloft into the atmosphere till the rarest of the vapour reaches the very cold regions of the air, which immediately forms a small portion of it into a fleecy cloud. This also further tempers the scorching heat by its opacity, performing the acceptable office of a screen. From thence the clouds are carried to the inland countries, to form the sources in the mountains which are to supply the numberless streams that water the fields. And by the steady operation of causes, which are tolerably uniform, the greater part of the vapours passes on to the circumpolar regions, there to descend in rains and dews; and by this beneficent conversion into rain by the cold of those regions, each particle of steam gives up the heat which was latent in it. This is immediately diffused, and softens the rigour of those less comfortable climates."

In the year 1766 Black was appointed Professor of Chemistry in the University of Edinburgh, in which position he remained till his death in 1799. During these thirty-three years he devoted himself chiefly to teaching and to encouraging the advance of chemical science. He was especially careful in the preparation of his elementary lectures, being persuaded that it was of the utmost importance that his pupils should be well grounded in the principles of chemistry.

His health had never been robust, and as he grew old he was obliged to use great care in his diet; his simple and methodical character and habits made it easy for him to live on the plainest food, and to take meals and exercise at stated times and in fixed quantities.

Black's life closed, as was fitting, in a quiet and honoured old age. He had many friends, but lived pretty much alone—he was never married.

On the 26th of November 1799, "being at table with his usual fare, some bread, a few prunes and a measured quantity of milk diluted with water, and having the cup in his hand when the last stroke of his pulse was to be given, he had set it down on his knees, which were joined together, and kept it steady with his hand, in the manner of a person perfectly at ease; and in this attitude he expired, without spilling a drop, and without a writhe in his countenance, as if an experiment had been required to show to his friends the facility with which he departed."

Black was characterized by "moderation and sobriety of thought;" he had a great sense of the fitness of things—of what is called by the older writers "propriety." But he was by no means a dull companion; he enjoyed general society, and was able to bear a part in any kind of conversation. A thorough student of Nature, he none the less did not wish to devote his whole time to laboratory work or to the labours of study; indeed he seems to have preferred the society of well-cultivated men and women to that of specialists in his own or other branches of natural science. But with his true scientific peers he doubtless appeared at his best. Among his more intimate friends were the famous political economist Adam Smith, and the no less celebrated philosopher David Hume. Dr. Hutton, one of the earliest workers in geology, was a particular friend of Black; his friendship with James Watt began when Watt was a student in his class, and continued during his life.

With such men as his friends, and engaged in the study of Nature—that boundless subject which one can never know to the full, but which one can always know a little more year by year—Black's life could not but be happy. His example and his teaching animated his students; he was what a university professor ought to be, a student among students, but yet a teacher among pupils. His work gained for him a place in the first rank of men of science; his clearness of mind, his moderation, his gentleness, his readiness to accept the views of others provided these views were well established on a basis of experimentally determined facts, fitted him to be the centre of a circle of scientific students who looked on him as at once their teacher and their friend.

As a lecturer Black was eminently successful. He endeavoured to make all his lectures plain and intelligible; he enlivened them by many experiments designed simply to illustrate the special point which he had in view. He abhorred ostentatious display and trickiness in a teacher.

Black was strongly opposed to the use of hypotheses in science. Dr. Robison (the editor of his lectures) tells that when a student in Edinburgh he met Black, who became interested in him from hearing him speak somewhat enthusiastically in favour of one of the lecturers in the university. Black impressed on him the necessity of steady experimental work in natural science, gave him a copy of Newton's "Optics" as a model after which scientific work ought to be conducted, and advised him "to reject, even without examination, any hypothetical explanation, as a mere waste of time and ingenuity." But, when we examine Black's own work, we see that by "hypothetical explanations" he meant vague guesses. He himself made free use of scientific (i.e. of exact) hypotheses; indeed the history of science tells us that without hypotheses advance is impossible. Black taught by his own researches that science is not an array of facts, but that the object of the student of Nature is to explain facts. But the method generally in vogue before the time of Black was to gather together a few facts, or what seemed to be facts, and on these to raise a vast superstructure of "vain imaginings." Naturalists had scarcely yet learned that Nature is very complex, and that guessing and reasoning on guesses, with here and there an observation added, was not the method by which progress was to be made in learning the lessons written in this complex book of Nature.

In place of this loose and slipshod method Black insisted that the student must endeavour to form a clear mental image of every phenomenon which he studied. Such an image could be obtained only by beginning with detailed observation and experiment. From a number of definite mental images the student must put together a picture of the whole natural phenomenon under examination; perceiving that something was wanted here, or that the picture was overcrowded there, he must again go to Nature and gain fresh facts, or sometimes prove that what had been accepted as facts had no real existence, and so at length he would arrive at a true representation of the whole process.

So anxious was Black to define clearly what he knew and professed to teach, that he preferred to call his lectures "On the Effects of Heat and Mixtures," rather than to announce them as "A Systematic Course on Chemistry."

His introductory lecture on "Heat in General" is very admirable; the following quotation will serve to show the clearness of his style and the methodical but yet eminently suggestive manner of his teaching:—

"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 illustrates 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 quantity, 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 entitled 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 assumed.

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 constituent 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 assistant 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 Cheshire, 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 Constitution 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 fortitude 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 publishing 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 circumstances, 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 glass, 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 glass or metal tubing passes 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.")