THE EXAMINATION OF THE PHENOMENA OF COMBUSTION.
The alchemists thought that the most effectual method of separating a
complex substance into more simple substances was to subject it to the
action of heat. They were constantly distilling, incinerating,
subliming, heating, in order that the spirit, or inner kernel of
things, might be obtained. They took for granted that the action of
fire was to simplify, and that simplification proceeded whatever might
be the nature of the substance which was subjected to this action.
Boyle insisted that the effect of heating one substance may be, and
often is, essentially different from the effect of heating another
substance; and that the behaviour of the same substance when heated,
sometimes varies when the conditions are changed. He takes the example
of heating sulphur or brimstone: "Exposed to a moderate fire in
subliming pots, it rises all into dry, and almost tasteless, flowers;
whereas being exposed to a naked fire, it affords store of a saline
and fretting liquor." Boyle thought that the action of fire was not
necessarily to separate a thing into its principles or elements, but,
in most cases, was either to rearrange the parts of the thing, so that
new, and it might be, more complex things, were produced, or to form
less simple things by the union of the substance with what he called,
"the matter of fire." When the product of heating a substance, for
example, tin or lead, weighed more than the substance itself, Boyle
supposed that the gain in weight was often caused by the "matter of
fire" adding itself to the substance which was heated. He commended to
the investigation of philosophers this "subtil fluid," which is "able
to pierce into the compact and solid bodies of metals, and add
something to them that has no despicable weight upon the balance, and
is able for a considerable time to continue fixed in the fire." Boyle
also drew attention to the possibility of action taking place between
a substance which is heated and some other substance, wherewith the
original thing may have been mixed. In a word, Boyle showed that the
alchemical assumption--fire simplifies--was too simple; and he taught,
by precept and example, that the only way of discovering what the
action of fire is, on this substance or on that, is to make accurate
experiments. "I consider," he says, "that, generally speaking, to
render a reason of an effect or phenomenon, is to deduce it from
something else in nature more known than itself; and that consequently
there may be divers kinds of degrees of explication of the same
thing."
Boyle published his experiments and opinions concerning the action of
fire on different substances in the seventies of the 17th century;
Stahl's books, which laid the foundation of the phlogistic theory, and
confirmed the alchemical opinion that the action of fire is
essentially a simplifying action, were published about forty years
later. But fifty years before Boyle, a French physician, named Jean
Rey, had noticed that the calcination of a metal is the production of
a more complex, from a less complex substance; and had assigned the
increase in weight which accompanies that operation to the attachment
of particles of the air to the metal. A few years before the
publication of Boyle's work, from which I have quoted, John Mayow,
student of Oxford, recounted experiments which led to the conclusion
that the air contains two substances, one of which supports combustion
and the breathing of animals, while the other extinguishes fire. Mayow
called the active component of the atmosphere _fiery air_; but he was
unable to say definitely what becomes of this fiery air when a
substance is burnt, although he thought that, in some cases, it
probably attaches itself to the burning substances, by which,
therefore, it may be said to be fixed. Mayow proved that the air
wherein a substance is burnt, or an animal breathes, diminishes in
volume during the burning, or the breathing. He tried, without much
success, to restore to air that part of it which disappears when
combustion, or respiration, proceeds in it.
What happens when a substance is burnt in the air? The alchemists
answered this question by asserting that the substance is separated or
analysed into things simpler than itself. Boyle said: the process is
not necessarily a simplification; it may be, and certainly sometimes
is, the formation of something more complicated than the original
substance, and when this happens, the process often consists in the
fixation of "the matter of fire" by the burning substance. Rey said:
calcination, of a metal at anyrate, probably consists in the fixation
of particles of air by the substance which is calcined. Mayow answered
the question by asserting, on the ground of the results of his
experiments, that the substance which is being calcined lays hold of a
particular constituent of the air, not the air as a whole.
Now, it is evident that if Mayow's answer was a true description of
the process of calcination, or combustion, it should be possible to
separate the calcined substance into two different things, one of
which would be the thing which was calcined, and the other would be
that constituent of the air which had united with the burning, or
calcining, substance. It seems clear to us that the one method of
proving the accuracy of Mayow's supposition must be, to weigh a
definite, combustible, substance--say, a metal; to calcine this in a
measured quantity of air; to weigh the product, and to measure the
quantity of air which remains; to separate the product of calcination
into the original metal, and a kind of air or gas; to prove that the
metal thus obtained is the same, and has the same weight, as the metal
which was calcined; and to prove that the air or gas obtained from the
calcined metal is the same, both in quality and quantity, as the air
which disappeared in the process of calcination.
This proof was not forthcoming until about a century after the
publication of Mayow's work. The experiments which furnished the proof
were rendered possible by a notable discovery made on the 1st of
August 1774, by the celebrated Joseph Priestley.
Priestley prepared many "airs" of different kinds: by the actions of
acids on metals, by allowing vegetables to decay, by heating beef,
mutton, and other animal substances, and by other methods. He says:
"Having procured a lens of twelve inches diameter and twenty inches
focal distance, I proceeded with great alacrity to examine, by the
help of it, what kind of air a great variety of substances, natural
and factitious, would yield.... With this apparatus, after a variety
of other experiments.... on the 1st of August, 1774, I endeavoured to
extract air from _mercurius calcinatus per se_; and I presently found
that, by means of this lens, air was expelled from it very readily.
Having got about three or four times as much as the bulk of my
materials, I admitted water to it, and found that it was not imbibed
by it. But what surprised me more than I can well express was, that a
candle burned in this air with a remarkably vigorous flame.... I was
utterly at a loss how to account for it."
[Illustration: FIG. XVI.]
The apparatus used by Priestley, in his experiments on different kinds
of air, is represented in Fig. XVI., which is reduced from an
illustration in Priestley's book on _Airs_.
Priestley had made a discovery which was destined to change Alchemy
into Chemistry. But he did not know what his discovery meant. It was
reserved for the greatest of all chemists, Antoine Lavoisier, to use
the fact stumbled on by Priestley.
After some months Priestley began to think it possible that the new
"air" he had obtained from calcined mercury might be fit for
respiration. To his surprise he found that a mouse lived in this air
much longer than in common air; the new air was evidently better, or
purer, than ordinary air. Priestley measured what he called the
"goodness" of the new air, by a process of his own devising, and
concluded that it was "between four and five times as good as common
air."
Priestley was a thorough-going phlogistean. He seems to have been able
to describe the results of his experiments only in the language of the
phlogistic theory; just as the results of most of the experiments made
to-day on the changes of compounds of the element carbon cannot be
described by chemists except by making use of the conceptions and the
language of the atomic and molecular theory.[6]
[6] I have given numerous illustrations of the truth of this
statement in the book, in this series, entitled _The Story of
the Wanderings of Atoms_.
The upholder of the phlogistic theory could not think of burning as
possible unless there was a suitable receptacle for the phlogiston of
the burning substance: when burning occurred in the air, the part
played by the air, according to the phlogistic chemist, was to receive
the expelled phlogiston; in this sense the air acted as the _pabulum_,
or nourishment, of the burning substance. Inasmuch as substances
burned more vigorously and brilliantly in the new air than in common
air, Priestley argued that the new air was more ready, more eager,
than ordinary air, to receive phlogiston; and, therefore, that the new
air contained less phlogiston than ordinary air, or, perhaps, no
phlogiston. Arguing thus, Priestley, of course, named the new aeriform
substance _dephlogisticated air_, and thought of it as ordinary air
deprived of some, or it might be all, of its phlogiston.
The breathing of animals and the burning of substances were supposed
to load the atmosphere with phlogiston. Priestley spoke of the
atmosphere as being constantly "vitiated," "rendered noxious,"
"depraved," or "corrupted" by processes of respiration and combustion;
he called those processes whereby the atmosphere is restored to its
original condition (or "depurated," as he said), "dephlogisticating
processes." As he had obtained his _dephlogisticated air_ by heating
the calx of mercury, that is the powder produced by calcining mercury
in the air, Priestley was forced to suppose that the calcination of
mercury in the air must be a more complex occurrence than merely the
expulsion of phlogiston from the mercury: for, if the process
consisted only in the expulsion of phlogiston, how could heating what
remained produce exceedingly pure ordinary air? It seemed necessary
to suppose that not only was phlogiston expelled from mercury during
calcination, but that the mercury also imbibed some portion, and that
the purest portion, of the surrounding air. Priestley did not,
however, go so far as this; he was content to suppose that in some
way, which he did not explain, the process of calcination resulted in
the loss of phlogiston by the mercury, and the gain, by the
dephlogisticated mercury, of the property of yielding exceedingly pure
or dephlogisticated air when it was heated very strongly.
Priestley thought of properties in much the same way as the alchemists
thought of them, as wrappings, or coverings of an essential something,
from which they can be removed and around which they can again be
placed. The protean principle of phlogiston was always at hand, and,
by skilful management, was ready to adapt itself to any facts. Before
the phenomena of combustion could be described accurately, it was
necessary to do two things; to ignore the theory of phlogiston, and to
weigh and measure all the substances which take part in some selected
processes of burning.
Looking back at the attempts made in the past to describe natural
events, we are often inclined to exclaim, "Why did investigators bind
themselves with the cords of absurd theories; why did they always wear
blinkers; why did they look at nature through the distorting mists
rising from their own imaginations?" We are too ready to forget the
tremendous difficulties which beset the path of him who is seeking
accurate knowledge.
"To climb steep hills requires slow pace at first."
Forgetting that the statements wherein the men of science of our own
time describe the relations between natural events are, and must be,
expressed in terms of some general conception, some theory, of these
relations; forgetting that the simplest natural occurrence is so
complicated that our powers of description are incapable of expressing
it completely and accurately; forgetting the uselessness of
disconnected facts; we are inclined to overestimate the importance of
our own views of nature's ways, and to underestimate the usefulness of
the views of our predecessors. Moreover, as naturalists have not been
obliged, in recent times, to make a complete renunciation of any
comprehensive theory wherein they had lived and moved for many years,
we forget the difficulties of breaking loose from a way of looking at
natural events which has become almost as real as the events
themselves, of abandoning a language which has expressed the most
vividly realised conceptions of generations of investigators, of
forming a completely new mental picture of natural occurrences, and
developing a completely new language for the expression of those
conceptions and these occurrences.
The younger students of natural science of to-day are beginning to
forget what their fathers told them of the fierce battle which had to
be fought, before the upholders of the Darwinian theory of the origin
of species were able to convince those for whom the older view, that
species are, and always have been, absolutely distinct, had become a
matter of supreme scientific, and even ethical, importance.
A theory which has prevailed for generations in natural science, and
has been accepted and used by everyone, can be replaced by a more
accurate description of the relations between natural facts, only by
the determination, labour, and genius of a man of supreme power. Such
a service to science, and humanity, was rendered by Darwin; a like
service was done, more than three-quarters of a century before Darwin,
by Lavoisier.
Antoine Laurent Lavoisier was born in Paris in 1743. His father, who
was a merchant in a good position, gave his son the best education
which was then possible, in physical, astronomical, botanical, and
chemical science. At the age of twenty-one, Lavoisier gained the prize
offered by the Government for devising an effective and economical
method of lighting the public streets. From that time until, on the
8th of May 1794, the Government of the Revolution declared, "The
Republic has no need of men of science," and the guillotine ended his
life, Lavoisier continued his researches in chemistry, geology,
physics, and other branches of natural science, and his investigations
into the most suitable methods of using the knowledge gained by
naturalists for advancing the welfare of the community.
In Chapter VI., I said that when an alchemist boiled water in an open
vessel, and obtained a white earthy solid, in place of the water which
disappeared, he was producing some sort of experimental proof of the
justness of his assertion that water can be changed into earth.
Lavoisier began his work on the transformations of matter by
demonstrating that this alleged transmutation does not happen; and he
did this by weighing the water, the vessel, and the earthy solid.
Lavoisier had constructed for him a pelican of white glass (see Fig.
XI., p. 88), with a stopper of glass. He cleaned, dried, and weighed
this vessel; then he put into it rain-water which he had distilled
eight times; he heated the vessel, removing the stopper from time to
time to allow the expanding air to escape, then put in the stopper,
allowed the vessel to cool, and weighed very carefully. The difference
between the second and the first weighing was the weight of water in
the vessel. He then fastened the stopper securely with cement, and
kept the apparatus at a temperature about 30° or 40° below that of
boiling water, for a hundred and one days. At the end of that time a
fine white solid had collected on the bottom of the vessel. Lavoisier
removed the cement from the stopper, and weighed the apparatus; the
weight was the same as it had been before the heating began. He
removed the stopper; air rushed in, with a hissing noise. Lavoisier
concluded that air had not penetrated through the apparatus during the
process of heating. He then poured out the water, and the solid which
had formed in the vessel, set them aside, dried, and weighed the
pelican; it had lost 17-4/10 grains. Lavoisier concluded that the
solid which had formed in the water was produced by the solvent action
of the water on the glass vessel. He argued that if this conclusion
was correct, the weight of the solid must be equal to the loss of
weight suffered by the vessel; he therefore separated the solid from
the water in which it was suspended, dried, and weighed it. The solid
weighed 4-9/10 grains. Lavoisier's conclusion seemed to be incorrect;
the weight of the solid, which was supposed to be produced by the
action of the water on the vessel, was 12-1/2 grains less than the weight
of the material removed from the vessel. But some of the material
which was removed from the vessel might have remained dissolved in the
water: Lavoisier distilled the water, which he had separated from the
solid, in a glass vessel, until only a very little remained in the
distilling apparatus; he poured this small quantity into a glass
basin, and boiled until the whole of the water had disappeared as
steam. There remained a white, earthy solid, the weight of which was
15-1/2 grains. Lavoisier had obtained 4-9/10 + 15-1/2 = 20-2/5 grains
of solid; the pelican had lost 17-2/5 grains. The difference between
these weights, namely, 3 grains, was accounted for by Lavoisier as due
to the solvent action of the water on the glass apparatus wherein it
had been distilled, and on the glass basin wherein it had been
evaporated to dryness.
Lavoisier's experiments proved that when distilled water is heated in
a glass vessel, it dissolves some of the material of the vessel, and
the white, earthy solid which is obtained by boiling down the water is
merely the material which has been removed from the glass vessel. His
experiments also proved that the water does not undergo any change
during the process; that at the end of the operation it is what it was
at the beginning--water, and nothing but water.
By this investigation Lavoisier destroyed part of the experimental
basis of alchemy, and established the one and only method by which
chemical changes can be investigated; the method wherein constant use
is made of the balance.
Lavoisier now turned his attention to the calcination of metals, and
particularly the calcination of tin. Boyle supposed that the increase
in weight which accompanies the calcination of a metal is due to the
fixation of "matter of fire" by the calcining metal; Rey regarded the
increase in weight as the result of the combination of the air with
the metal; Mayow thought that the atmosphere contains two different
kinds of "airs," and one of these unites with the heated metal.
Lavoisier proposed to test these suppositions by calcining a weighed
quantity of tin in a closed glass vessel, which had been weighed
before, and should be weighed after, the calcination. If Boyle's view
was correct, the weight of the vessel and the tin would be greater at
the end than it was at the beginning of the operation; for "matter of
fire" would pass through the vessel and unite with the metal. If there
was no change in the total weight of the apparatus and its contents,
and if air rushed in when the vessel was opened after the calcination,
and the total weight was then greater than at the beginning of the
process, it would be necessary to adopt either the supposition of Rey
or that of Mayow.
Lavoisier made a series of experiments. The results were these: there
was no change in the total weight of the apparatus and its contents;
when the vessel was opened after the calcination was finished, air
rushed in, and the whole apparatus now weighed more than it did before
the vessel was opened; the weight of the air which rushed in was
exactly equal to the increase in the weight of the tin produced by the
calcination, in other words, the weight of the inrushing air was
exactly equal to the difference between the weights of the tin and the
calx formed by calcining the tin. Lavoisier concluded that to calcine
tin is to cause it to combine with a portion of the air wherein it is
calcined. The weighings he made showed that about one-fifth of the
whole weight of air in the closed flask wherein he calcined tin had
disappeared during the operation.
Other experiments led Lavoisier to suspect that the portion of the air
which had united with the tin was different from the portion which had
not combined with that metal. He, therefore, set himself to discover
whether there are different kinds of "airs" in the atmosphere, and, if
there is more than one kind of "air," what is the nature of that "air"
which combines with a metal in the process of calcination. He proposed
to cause a metallic calx (that is, the substance formed by calcining
a metal in the air) to give up the "air" which had been absorbed in
its formation, and to compare this "air" with atmospheric air.
About this time Priestley visited Paris, saw Lavoisier, and told him
of the new "air" he had obtained by heating calcined mercury.
Lavoisier saw the great importance of Priestley's discovery; he
repeated Priestley's experiment, and concluded that the air, or gas,
which he refers to in his Laboratory Journal as "l'air dephlogistique
de M. Priestley" was nothing else than the purest portion of the air
we breathe. He prepared this "air" and burned various substances in
it. Finding that very many of the products of these combustions had
the properties of acids, he gave to the new "air" the name _oxygen_,
which means _the acid-producer_.
At a later time, Lavoisier devised and conducted an experiment which
laid bare the change of composition that happens when mercury is
calcined in the air. He calcined a weighed quantity of mercury for
many days in a measured volume of air, in an apparatus arranged so
that he was able to determine how much of the air disappeared during
the process; he collected and weighed the red solid which formed on
the surface of the heated mercury; finally he heated this red solid to
a high temperature, collected and measured the gas which was given
off, and weighed the mercury which was produced. The sum of the
weights of the mercury and the gas which were produced by heating the
calcined mercury was equal to the weight of the calcined mercury; and
the weight of the gas produced by heating the calcined mercury was
equal to the weight of the portion of the air which had disappeared
during the formation of the calcined mercury. This experiment proved
that the calcination of mercury in the air consists in the combination
of a constituent of the air with the mercury. Fig. XVII. (reduced from
an illustration in Lavoisier's Memoir) represents the apparatus used
by Lavoisier. Mayow's supposition was confirmed.
[Illustration: FIG. XVII.]
Lavoisier made many more experiments on combustion, and proved that in
every case the component of the atmosphere which he had named oxygen
combined with the substance, or with some part of the substance, which
was burned. By these experiments the theory of Phlogiston was
destroyed; and with its destruction, the whole alchemical apparatus of
Principles and Elements, Essences and Qualities, Souls and Spirits,
disappeared.