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The Story of Alchemy and the Beginnings of Chemistry

Chapter 15

part in the processes. He was especially desirous they should consider

what part the air might play in calcinations; he spoke of the air as a "menstruum or additament," and said that, in such operations as calcination, "We may well take the freedom to examine ... whether there intervene not a coalition of the parts of the body wrought upon with those of the menstruum, whereby the produced concrete may be judged to result from the union of both." It was by examining the part played by the air in processes of calcination and burning that men at last became able to give approximately complete descriptions of these processes. Boyle recognised that the air is not a simple or elementary substance; he spoke of it as "a confused aggregate of effluviums from such differing bodies, that, though they all agree in constituting by their minuteness and various motions one great mass of fluid matter, yet perhaps there is scarce a more heterogeneous body in the world." Clement of Alexandria who lived in the end of the 2nd, and the early part of the 3rd, century A.D., seems to have regarded the air as playing a very important part in combustions; he said--"Airs are divided into two categories; an air for the divine flame, which is the soul; and a material air which is the nourisher of sensible fire, and the basis of combustible matter." Sentences like that I have just quoted are found here and there in the writings of the earlier and later alchemists; now and again we also find statements which may be interpreted, in the light of the fuller knowledge we now have, as indicating at least suspicions that the atmosphere is a mixture of different kinds of air, and that only some of these take part in calcining and burning operations. Those suspicions were confirmed by experiments on the calcination of metals and other substances, conducted in the 17th century by Jean Rey a French physician, and by John Mayow of Oxford. But these observations and the conclusions founded on them, did not bear much fruit until the time of Lavoisier, that is, towards the close of the 18th century. They were overshadowed and put aside by the work of Stahl (1660-1724). Some of the alchemists of the 14th, 15th and 16th centuries taught that combustion and calcination are processes wherein _the igneous principle_ is destroyed, using the word "destroyed" in its alchemical meaning. This description of processes of burning was much more in keeping with the ideas of the time than that given by Boyle, Rey and Mayow. It was adopted by Stahl, and made the basis of a general theory of those changes wherein one substance disappears and another, or others, very unlike it, are produced. That he might bring into one point of view, and compare the various changes effected by the agency of fire, Stahl invented a new Principle, which he named _Phlogiston_, and constructed an hypothesis which is generally known as the phlogistic theory. He explained, and applied, this hypothesis in various books, especially in one published at Halle in 1717. Stahl observed that many substances which differed much from one another in various respects were alike in one respect; they were all combustible. All the combustible substances, he argued, must contain a common principle; he named this supposed principle, _phlogiston_ (from the Greek word _phlogistos_ = burnt, or set on fire). Stahl said that the phlogiston of a combustible thing escapes as the substance burns, and, becoming apparent to the senses, is named fire or flame. The phlogiston in a combustible substance was supposed to be so intimately associated with something else that our senses cannot perceive it; nevertheless, the theory said, it is there; we can see only the escaping phlogiston, we can perceive only the phlogiston which is set free from its combination with other things. The theory thought of phlogiston as imprisoned in the thing which can be burnt, and as itself forming part of the prison; that the prisoner should be set free, the walls of the prison had to be removed; the freeing of the prisoner destroyed the prison. As escaping, or free, phlogiston was called fire, or flame, so the phlogiston in a combustible substance was sometimes called combined fire, or flame in the state of combination. A peculiarity of the strange thing called phlogiston was that it preferred to be concealed in something, hidden, imprisoned, combined; free phlogiston* was supposed to be always ready to become combined phlogiston. *Transcriber's Note: Original "phlogstion". The phlogistic theory said that what remains when a substance has been burnt is the original substance deprived of phlogiston; and, therefore, to restore the phlogiston to the product of burning is to re-form the combustible substance. But how is such a restoration of phlogiston to be accomplished? Evidently by heating the burnt thing with something which is very ready to burn. Because, according to the theory, everything which can be burnt contains phlogiston, the more ready a substance is to burn the richer it is in phlogiston; burning is the outrush of phlogiston, phlogiston prefers to be combined with something; therefore, if you mix what remains after burning, with something which is very combustible, and heat the mixture, you are bringing the burnt matter under conditions which are very favourable for the reception of phlogiston by it, for you are bringing it into intimate contact with something from which freedom-hating phlogiston is being forced to escape. Charcoal, sulphur, phosphorus, oils and fats are easily burnt; these substances were, therefore, chosen for the purpose of changing things which had been burnt into things which could again be burnt; these, and a few other substances like these, were classed together, and called _phlogisticating agents_. Very many of the substances which were dealt with by the experimenters of the last quarter of the 17th, and the first half of the 18th, century, were either substances which could be burned, or those which had been produced by burning; hence the phlogistic theory brought into one point of view, compared, and emphasised the similarities between, a great many things which had not been thought of as connected before that theory was promulgated. Moreover, the theory asserted that all combustible, or incinerable, things are composed of phlogiston, and another principle, or, as was often said, another element, which is different in different kinds of combustible substances. The metals, for instance, were said to be composed of phlogiston and an earthy principle or element, which was somewhat different in different metals. The phlogisteans taught that the earthy principle of a metal remains in the form of ash, cinders, or calx, when the metal is calcined, or, as they expressed it, when the metal is deprived of its phlogiston. The phlogistic theory savoured of alchemy; it postulated an undefined, undefinable, intangible Principle; it said that all combustible substances are formed by the union of this Principle with another, which is sometimes of an earthy character, sometimes of a fatty nature, sometimes highly volatile in habit. Nevertheless, the theory of Stahl was a step away from purely alchemical conceptions towards the accurate description of a very important class of changes. The principle of phlogiston could be recognised by the senses as it was in the act of escaping from a substance; and the other principle of combustible things was scarcely a Principle in the alchemical sense, for, in the case of metals at any rate, it remained when the things which had contained it were burnt, and could be seen, handled, and weighed. To say that metals are composed of phlogiston and an earthy substance, was to express facts in such a language that the expression might be made the basis of experimental inquiry; it was very different from the assertion that metals are produced by the spiritual actions of the three Principles, salt, mercury and sulphur, the first of which is not salt, the second is not mercury, and the third is not sulphur. The followers of Stahl often spoke of metals as composed of phlogiston and an _element_ of an earthy character; this expression also was an advance, from the hazy notion of _Element_ in purely alchemical writings, towards accuracy and fulness of description. An element was now something which could he seen and experimented with; it was no longer a semi-spiritual existence which could not be grasped by the senses. The phlogistic theory regarded the calcination of a metal as the separation of it into two things, unlike the metal, and unlike each other; one of these things was phlogiston, the other was an earth-like residue. The theory thought of the re-formation of a metal from its calx, that is, the earthy substance which remains after combustion, as the combination of two things to produce one, apparently homogeneous, substance. Metals appeared to the phlogisteans, as they appeared to the alchemists, to be composite substances. Processes of burning were regarded by alchemists and phlogisteans alike, as processes of simplification. The fact had been noticed and recorded, during the middle ages, that the earth-like matter which remains when a metal is calcined is heavier than the metal itself. From this fact, modern investigators of natural phenomena would draw the conclusion, that calcination of a metal is an addition of something to the metal, not a separation of the metal into different things. It seems impossible to us that a substance should be separated into portions, and one of these parts should weigh as much as, or more than, the whole. The exact investigation of material changes called chemistry rests on the statement that _mass_, and mass is practically measured by _weight_, is the one property of what we call matter, the determination whereof enables us to decide whether a change is a combination, or coalescence, of different things, or a separation of one thing into parts. That any part of a material system can be removed without the weight of the portion which remains being less than the original weight of the whole system, is unthinkable, in the present state of our knowledge of material changes. But in the 17th century, and throughout most of the 18th, only a few of those who examined changes in the properties of substances paid heed to changes of weight; they had not realised the importance of the property of mass, as measured by weight. The convinced upholder of the phlogistic theory had two answers to the argument, that, because the earth-like product of the calcination of a metal weighs more than the metal itself, therefore the metal cannot have lost something in the process; for, if one portion of what is taken away weighs more than the metal from which it has been separated, it is evident that the weight of the two portions into which the metal is said to have been divided must be considerably greater than the weight of the undivided metal. The upholders of the theory sometimes met the argument by saying, "Of course the calx weighs more than the metal, because phlogiston tends to lighten a body which contains it; and therefore the body weighs more after it has lost phlogiston than it did when the phlogiston formed part of it;" sometimes, and more often, their answer was--"loss or gain of weight is an accident, the essential thing is change of qualities." If the argument against the separation of a metal into two constituents, by calcination, were answered to-day as it was answered by the upholders of the phlogistic theory, in the middle of the 18th century, the answers would justly be considered inconsequent and ridiculous. But it does not follow that the statements were either far-fetched or absurd at the time they were made. They were expressed in the phraseology of the time; a phraseology, it is true, sadly lacking in consistency, clearness, and appropriateness, but the only language then available for the description of such changes as those which happen when metals are calcined. One might suppose that it must always have sounded ridiculous to say that the weight of a thing can be decreased by adding something to it, that part of a thing weighs more than the whole of it. But the absurdity disappears if it can be admitted that mass, which is measured by weight, may be a property like colour, or taste, or smell; for the colour, taste, or smell of a thing may certainly be made less by adding something else, and the colour, taste, or smell of a thing may also be increased by adding something else. If we did not know that what we call _quantity of substance_ is measured by the property named _mass_, we might very well accept the proposition that the entrance of phlogiston into a substance decreases the quantity, hence the mass, and, therefore, the weight, of the substance. Although Stahl and his followers were emerging from the trammels of alchemy, they were still bound by many of the conceptions of that scheme of nature. We have learned, in previous chapters, that the central idea of alchemy was expressed in the saying: "Matter must be deprived of its properties in order to draw out its soul." The properties of substances are everything to the modern chemist--indeed, such words as iron, copper, water, and gold are to him merely convenient expressions for certain definable groups of properties--but the phlogisteans regarded the properties of things, including mass, as of secondary importance; they were still trying to get beneath the properties of a thing, to its hypothetical essence, or substance. Looking back, we cannot think of phlogiston as a substance, or as a thing, in the modern meanings of these terms as they are used in natural science. Nowadays we think, we are obliged to think, of the sum of the quantities of all the things in the universe as unchanging, and unchangeable by any agency whereof we have definite knowledge. The meaning we give to the word _thing_ rests upon the acceptance of this hypothesis. But the terms _substance_, _thing_, _properties_ were used very vaguely a couple of centuries ago; and it would be truly absurd to carry back to that time the meanings which we give to these terms to-day, and then to brand as ridiculous the attempts of the men who studied, then, the same problems which we study now, to express the results of their study in generalisations which employed the terms in question, in what seems to us a loose, vague, and inexact manner. By asserting, and to some extent experimentally proving, the existence of one principle in many apparently very different substances (or, as would be said to-day, one property common to many substances), the phlogistic theory acted as a very useful means for collecting, and placing in a favourable position for closer inspection, many substances which would probably have remained scattered and detached from one another had this theory not been constructed. A single assumption was made, that all combustible substances are alike in one respect, namely, in containing combined fire, or phlogiston; by the help of this assumption, the theory of phlogiston emphasised the fundamental similarity between all processes of combustion. The theory of phlogiston was extraordinarily simple, compared with the alchemical vagaries which preceded it. Hoefer says, in his _Histoire de la Chimie_, "If it is true that simplicity is the distinctive character of verity, never was a theory so true as that of Stahl." The phlogistic theory did more than serve as a means for bringing together many apparently disconnected facts. By concentrating the attention of the students of material changes on one class of events, and giving descriptions of these events without using either of the four alchemical Elements, or the three Principles, Stahl, and those who followed him, did an immense service to the advancement of clear thinking about natural occurrences. The principle of phlogiston was more tangible, and more readily used, than the Salt, Sulphur, and Mercury of the alchemists; and to accustom people to speak of the material substance which remained when a metal, or other combustible substance, was calcined or burnt, as one of the _elements_ of the thing which had been changed, prepared the way for the chemical conception of an element as a definite substance with certain definite properties. In addition to these advantages, the phlogistic theory was based on experiments, and led to experiments, the results of which proved that the capacity to undergo combustion might be conveyed to an incombustible substance, by causing it to react with some other substance, itself combustible, under definite conditions. The theory thus prepared the way for the representation of a chemical change as an interaction between definite kinds of substances, marked by precise alterations both of properties and composition. The great fault of the theory of phlogiston, considered as a general conception which brings many facts into one point of view, and leads the way to new and exact knowledge, was its looseness, its flexibility. It was very easy to make use of the theory in a broad and general way; by stretching it here, and modifying it there, it seemed to cover all the facts concerning combustion and calcination which were discovered during two generations after the publication of Stahl's books. But many of the subsidiary hypotheses which were required to make the theory cover the new facts were contradictory, or at any rate seemed to be contradictory, of the primary assumptions of the theory. The addition of this ancillary machinery burdened the mechanism of the theory, threw it out of order, and finally made it unworkable. The phlogistic theory was destroyed by its own cumbersomeness. A scientific theory never lasts long if its fundamental assumptions are stated so loosely that they may be easily modified, expanded, contracted, and adjusted to meet the requirements of newly discovered facts. It is true that the theories which have been of the greatest service in science, as summaries of the relations between established facts, and suggestions of lines of investigation, have been stated in terms whose full meaning has gradually unfolded itself. But the foundations of these theories have been at once so rigidly defined and clearly stated as to be incapable of essential modification, and so full of meaning and widely applicable as to cover large classes of facts which were unknown when the theories were constructed. Of the founders of the lasting and expansible theories of natural science, it may be said, that "thoughts beyond their thoughts to those high bards were given."