Chapter XI (1)

Priestley as a man of science--His characteristics as a
philosopher--_Experiments and Observations on Different Kinds of
Air_--His discovery of the influence of vegetation on vitiated
air--Atmospheric air not elementary--His researches on nitric
oxide--Eudiometry--Nitrous oxide--Discovers hydrogen
chloride--Prepares oxygen from nitre (1771)--Isolates ammonia
gas--Discovers sulphur dioxide--Dephlogisticated air
(oxygen)--Discovers silicon fluoride--Intra-diffusion of
gases--Respiration--Priestley's opinions of the value of experimental
science in education--Discovers nitrosulphuric acid--Notes the
constancy of composition of the atmosphere--Prepares chlorine--Sound
in "air"--Experiments relating to phlogiston--The seeming conversion
of water into air--Watt and the compound nature of water--Discovers
sulphuretted hydrogen--Priestley's confession of faith in phlogiston.

Priestley's position in the history of science mainly rests on his discoveries in pneumatic chemistry. The course of inquiry which he began at Leeds was continued by him, with characteristic assiduity and conspicuous success, at Calne, and his labours added largely to the number of the aeriform bodies which were clearly recognised as distinct substances, essentially differing from each other, and not merely modifications of a common principle, modified or affected by properties more or less fortuitous and accidental. The old idea of the nature of "air" had its origin in the doctrine of the Four Elements. It is Priestley's merit that he, more than any man of his time, contributed to the overthrow of this conception as the basis of a philosophical system of the constitution of the material universe. Although Priestley could not be unmindful that his claim to scientific fame was to be found in the succession of volumes which he called _Experiments and Observations on Different Kinds of Air_, the very title suggests that he, at all events in the outset, was hardly conscious of the magnitude and true significance of his work. Priestley was in no real sense a speculative philosopher: he was indeed pre-eminently the type of man whom Hobbes disparaged as an "experimentarian philosopher," and an experimentarian philosopher he remained to the end of his days. He was aware of his limitations, and many passages from his works, and especially from his correspondence, might be quoted in proof of this fact. His simple, unaffected candour was indeed one of the charms of his character and the secret of much of his influence. It is reflected in every page of his scientific writings. His own discoveries, taken collectively, did more than those of any one of his contemporaries to uproot and destroy the only generalisation by which his immediate predecessors had sought to group and connect the phenomena of chemistry, but he was wholly unable to perceive this fact. A patient and industrious observer, absolutely truthful, and, as he hoped and believed, unbiassed and impartial, he was nevertheless entirely lacking in the higher qualities of the imagination or in that power of divination which is the characteristic of men of the type of Newton. The contrast between Priestley--the social, political and theological reformer, always in advance of his times, receptive, fearless and insistent; and Priestley the man of science--timorous and halting when he might well be bold, conservative and orthodox when almost every other active worker was heterodox and progressive--is most striking. And yet, such is the irony of circumstance, Priestley's name mainly lives as that of a chemical philosopher. When men have desired to do him honour, and have sought to perpetuate his memory by statues in public places, he is generally represented as making a chemical experiment. In reality, great as Priestley's merit is as an experimentarian philosopher, his greater claim on our regard and esteem rests upon his struggles and his sufferings in the cause of civil, political and religious liberty.

The years which Priestley spent at Calne constitute the most fruitful period of his scientific career. Practically all that he did in the way of solid achievement and of addition to the armoury of science was effected during that time. Although, after leaving Lord Shelburne, he continued to pursue scientific inquiry with his wonted zeal and industry, doubtless adding thereby to his fame among his contemporaries, posterity has set the true measure of appreciation to his later efforts. He doubtless made many hundreds of experiments in connection with more or less well-defined trains of inquiry; nevertheless, it cannot be maintained that during his subsequent period he added many first-rate facts to our knowledge, or indeed discovered any facts at all comparable in importance with those he ascertained during his life in Wiltshire. On the contrary, what he did observe--as for example the seeming conversion of water into air--too frequently led him astray and was the cause of error to himself and others. Thus Watt's claim to be considered as an independent, if not the first and true, discoverer of the real chemical nature of water is based upon Priestley's experimental blunders. Watt was undoubtedly accurate in his surmise, but the surmise was right in spite of, and not by reason of, Priestley's experimental evidence. Priestley recorded his experiments with such fulness that it is now easy to perceive where he went wrong. He was constantly on the verge of a discovery, sometimes indeed of a discovery of cardinal importance, but as constantly it eluded his grasp. The experiments on the seeming conversion of water into air might have led him, when he got over his chagrin on the detection of the real cause of his error, to the recognition of the underlying truth in it, namely, the principle of the diffusion of gases. He was, of course, familiar with the fact that the various gases he discovered, or which were known to him, differed in relative density, and he knew perfectly well that they tended to escape from the bottles in which they were contained if these were uncovered and freely exposed to the air. But, so far as we can learn, he never seems to have pondered on these facts, or noted their connection with the phenomena he observed in the course of his many experiments with Wedgwood's retorts, and of the interchange of the water vapour he introduced into them with the gases of the fire which heated them. And yet, had he perceived even a glimmer of the truth he had sufficient means at his disposal, and sufficient knowledge from his own work and that of his contemporaries, to make the great step which it was reserved to Graham to accomplish half a century later.

Whilst the chief importance of the _Experiments and Observations on Different Kinds of Air_ is that it is Priestley's _magnum opus_, to his biographer it has the additional interest of affording an insight into the personal character and intellectual attributes of its author. Few writers on scientific subjects have ever taken their readers so completely into their confidence as Priestley. Whatever he knows or thinks he tells: doubts, perplexities, blunders are set down with the most refreshing candour; one forgives the prolixity and occasional tediousness, even the little touches of self-satisfaction, in view of the transparent honesty of purpose, the single-minded pursuit of truth for its own sake, wholly apart from preconception or bias of dogma which shine on every page. As key-notes to character, even the dedications and prefaces to the several volumes have their peculiar value and charm, as evidence of the workings of an ingenuous mind.

The publication of the six volumes comprising the original work--the edition of greatest value to Priestley's biographer--extended from 1775 to 1786. Although the space at our disposal precludes any attempt at a full account of the contents, it is necessary to set these out in such detail as may serve to afford a just idea of their value, and with such comment as may be necessary to elucidate their significance.

In the preface to the first volume, which made its appearance in 1775, with a dedication to Lord Shelburne, Priestley thinks it necessary to explain why he has decided, contrary to his original intention, but with the approbation of the President and of his friends in the Royal Society, not to send them any more papers on the subject of "Air" at present but to make immediate publication of all he has done with respect to it. In view, he says, of the rapid progress that has been made and may be expected to be made in this branch of knowledge, "unnecessary delays in the publication of experiments relating to it are peculiarly unjustifiable."

"When, for the sake of a little more reputation, men can keep brooding
over a new fact, in the discovery of which they might possibly have
very little real merit, till they think they can astonish the world
with a system as complete as it is new, and give mankind a prodigious
idea of their judgment and penetration, they are justly punished for
their ingratitude to the fountain of all knowledge, and for the want
of a genuine love of science and of mankind in finding their boasted
discoveries anticipated and the field of honest fame pre-occupied by
men who, from a natural ardour of mind, engage in philosophical
pursuits, and with an ingenuous simplicity immediately communicate to
others whatever occurs to them in their inquiries."

Priestley's productions, from the very nature of the case make no pretensions to completeness.

"In completing one discovery we never fail to get an imperfect
knowledge of others of which we could have no idea before, so that we
cannot solve one doubt without creating several new ones."

He farther observes that a person who means to serve the cause of science effectually must hazard his own reputation so far as to risk even _mistakes_ in things of less moment.

"Among a multiplicity of new objects and new relations some will
necessarily pass without sufficient attention; but if a man be not
mistaken in the principal objects of his pursuits he has no occasion
to distress himself about lesser things.

"In the progress of his inquiries he will generally be able to rectify
his own mistakes; or if little and envious souls should take a
malignant pleasure in detecting them for him and endeavouring to
expose him, he is not worthy of the name of a philosopher if he has
not strength of mind sufficient to enable him not to be disturbed at
it. He who does not foolishly affect to be above the failings of
humanity will not be mortified when it is proved that he is but a
man."

He made it a rule to disclose the real views with which he made his experiments. Although, he says, by following a contrary maxim he might have acquired a character of greater sagacity, he thought that two good ends were secured by his method--one as tending to make his narrative more interesting, and the other as encouraging other adventurers in experimental philosophy by showing them that by pursuing even false lights real and important truths may be discovered, and that in seeking one thing we often find another. He believes, however, that he writes more concisely than is usual with those who publish accounts of their experiments, and in thus refraining from swelling his book "to a pompous and respectable size" he trusts he will earn the gratitude of those philosophers who, having but little time to spare for _reading_, which is always the case with those who _do_ much themselves, will thereby be kept not too long from their own pursuits. He then comments on what he justly considers the amazing improvements in natural knowledge which have been made within the century, and contrasts these with the comparative poverty as regards scientific results of the many preceding ages, which yet abounded with men who had no other object but study; and he rejoices to think that this rapid progress of knowledge, extending itself not this way or that way only, but in all directions, will be the means of extirpating all error and prejudice and of putting an end to all undue and usurped authority in the business of religion as well as of science.

"It was ill policy in Leo the Tenth to patronise polite literature. He
was cherishing an enemy in disguise. And the English hierarchy (if
there be anything unsound in its constitution) has equal reason to
tremble even at an air-pump or an electrical machine."

He regrets that the rich and great in this country, unmindful of the example of Bacon, give less attention to these matters than do men of rank and fortune in other countries: he contrasts the pleasure of the pursuit of science with the pains and penalties of the pursuit of politics.

"If extensive and lasting fame be at all an object, literary, and
especially scientifical, pursuits are preferable to political ones in
a variety of respects.... If extensive usefulness be the object,
science has the same advantage over politics. The greatest success in
the latter seldom extends farther than one particular country and one
particular age, whereas a successful pursuit of science makes a man
the benefactor of all mankind and of every age. How trifling is the
fame of any statesman that this country has ever produced to that of
Lord Bacon, of Newton, or of Boyle; and how much greater are our
obligations to such men as these than to any other in the whole
_Biographia Britannica_."

It would be interesting to know the sentiments of Lord Shelburne, then in the cold shade of retirement, as he perused these passages, and whether he realised the truth of the little homily from his "tame philosopher."

The preface is followed by an introduction, in which Priestley gives a rapid and confessedly imperfect survey of the state of knowledge concerning "air" prior to 1774. He gives to Boyle the credit of first clearly recognising that elastic fluids exist differing essentially from the air of the atmosphere, but agreeing with it in the properties of weight, elasticity and transparency. But he also points out that two remarkable kinds of factitious air had long been known to miners, viz., _choke damp_, which is heavier than air, which lies at the bottom of pits, extinguishes flame and kills animals; and the other, called _fire damp_, which is lighter than common air, is found, therefore, near the roofs of subterraneous places and is liable to take fire and explode like gunpowder. "The word _damp_ signifies _vapour_ or _exhalation_ in the German and Saxon languages."

"Air of the former kind, besides having been discovered in various
caverns, particularly the Grotta del Cane in Italy, had also been
observed on the surface of fermenting liquors, and had been called
_gas_ (which is the same with _geist_, or _spirit_) by Van Helmont and
other German chemists; but afterwards it obtained the name of _fixed
air_, especially after it had been discovered by Dr Black of Edinburgh
to exist, in a fixed state, in alkaline salts, chalk, and other
calcareous substances."

Black's work is dealt with in half a dozen lines, and a passing reference is made to Macbride and Brownrigg. A very imperfect account is given of the work of Hales, although it is stated that "his experiments are so numerous and various that they are justly esteemed to be the solid foundation of all our knowledge of this subject." This section concludes with the mention of Cavendish's determinations of the relative weights of fixed air (carbon dioxide), and inflammable air from metals (hydrogen), and of Lane's observations that water charged with carbonic acid will dissolve iron, "and thereby become a strong chalybeate."

Priestley was the last man in the world to seek to disparage the work of his predecessors or to minimise what was due to them. In reality he had the intention, as he distinctly states, to write at his leisure the history and present state of discoveries relating to air, in a manner similar to his _History of Electricity_, and of the _Discoveries Relating to Vision, Light and Colours_, when no doubt he would have done full justice to all concerned. In the meantime he gives only such particulars as are necessary, in his judgment, to the understanding of his own work.

The remaining section of the introduction deals with his method of experimenting and with the apparatus he employed. It is of historical interest as containing a description of that most useful article of chemical furniture, his well-known pneumatic trough. He explains its use and gives details of his modes of manipulation. What an advance these were in simplicity, ingenuity and convenience can only be fully realised by comparing his methods with those of Hales. Not the least of Priestley's services to science were the improvements he effected in that section of operative chemistry which is concerned with the preparation, collection and storage of gaseous substances.

The main body of the volume is divided into two parts--the first dealing with observations made in and before 1772, the second with observations made in the year 1773 and in the beginning of 1774. In the outset Priestley finds himself at a disadvantage in regard to the only terms at that time in vogue for the factitious airs, viz., _fixed_, _mephitic_ and _inflammable_, which, he rightly says, are not sufficiently characteristic and distinct. Strictly speaking, any two of these terms might be applied to any one of the "airs" then known. The inflammable air from metals, as well as choke damp, is noxious, and therefore mephitic, as is fixed air, and since the inflammable airs are, apparently, capable of being imbibed by certain substances they may equally be considered fixable. The term _fixed air_ had, however, acquired a distinctive meaning, and rather than introduce a new term or change the signification of an old one, he would, with his contemporaries, restrict the term to the air which had been made the subject of Black's memorable investigation. The first paper in this section deals with fixed air; it is practically a reprint of that in the _Phil. Trans._ and which has already been described in sufficient detail. In the course of his experiments he says he once thought that the readiest method of procuring fixed air, and in sufficient purity, would be to heat pounded lime-stone in a gun barrel, "making it pass through the stem of a tobacco pipe or a glass tube carefully luted to the orifice of it."

"In this manner I found that air is produced in great plenty; but,
upon examining it, I found to my great surprise that little more than
one half of it was fixed air, capable of being absorbed by water; and
that the rest was inflammable, sometimes very weakly, but sometimes
pretty highly so."

He surmised that this "air" must come from the iron, and yet, he noted, it differed from the ordinary inflammable air from iron by the remarkable blue colour of its flame, and he concludes that "this inflammable principle may come from some remains of the animals from which it is thought that all calcareous matter proceeds." Priestley, we now know, had incidentally converted some of the fixed air into the only other oxide of carbon, but he failed to appreciate the significance of his observation, and the credit of the discovery of carbon monoxide belongs to Cruikshank.

In his next paper on "Air in which Candles have burned," Priestley made a discovery of the very highest importance. He had attempted to verify without success the allegation by the Count de Saluce, made in the memoirs of the Philosophical Society of Turin, that air vitiated by the combustion of candles could be restored by exposure to cold.

"Though this experiment failed," he says, "I have been so happy as by
accident to have hit upon a method of restoring air which has been
injured by the burning of candles, and to have discovered at least one
of the restoratives which Nature employs for this purpose. It is
_vegetation_. This restoration of vitiated air, I conjecture, is
effected by plants imbibing the phlogistic matter with which it is
overloaded by the burning of inflammable bodies. But whether there be
any foundation for this conjecture or not, the fact is, I think,
indisputable."

He then proceeds to give an account of his observations on the growing of plants in confined air which led to his discovery.

"One might have imagined," he says, "that since common air is
necessary to vegetable as well as to animal life, both plants and
animals had affected it in the same manner; and I own I had that
expectation when I first put a sprig of mint into a glass jar standing
inverted in a vessel of water: but when it had continued there for
some months I found the air would neither extinguish the candle, nor
was it at all inconvenient to a mouse, which I put into it.... Finding
that candles would burn very well in air in which plants had grown a
long time, and having had some reason to think that there was
something attending vegetation which restored air that had been
injured by respiration, I thought it was possible that the same
process might also restore the air that had been injured by the
burning of candles.

"Accordingly, on the 17th of August 1771, I put a sprig of mint into a
quantity of air in which a wax candle had burned out, and found that
on the 27th of the same month another candle burned perfectly well in
it. This experiment I repeated, without the least variation in the
event, not less than eight or ten times in the remainder of the
summer.

"Several times I divided the quantity of air in which the candle had
burned out into two parts, and putting the plant into one of them left
the other in the same exposure, contained also in a glass vessel
immersed in water, but without any plant, and never failed to find
that a candle would burn in the former but not in the latter.... This
remarkable effect does not depend upon anything peculiar to _mint_,
which was the plant that I always made use of till July 1772; for on
the 16th of that month I found a quantity of this kind of air to be
perfectly restored by sprigs of _balm_, which had grown in it from the
7th of the same month.

"That this restoration of air was not owing to any aromatic effluvia
of these two plants not only appeared by the _essential oil of mint_
having no sensible effect of this kind, but from the equally complete
restoration of this vitiated air by the plant called _groundsel_,
which is usually ranked among the weeds and has an offensive smell.
Besides, the plant which I have found to be the most effectual of any
that I have tried for this purpose is _spinach_, which is of quick
growth, but will seldom thrive long in water."

The next paper on "Inflammable Air" is of slight importance, and indeed is full of errors. Priestley made no distinction between the inflammable air obtained by the action of acids on metals (hydrogen) and that formed by the destructive distillation of coal and other organic substances (marsh gas or carbonic oxide, or mixtures of the two), and his inability to distinguish these different gases accounts for many of the phenomena he observed and which he confesses himself unable to explain. The most sagacious observation in the memoir has reference to the colour of the electric spark in the different gases which he accurately describes.

The paper on "Air Infected with Animal Respiration or Putrefection" may be considered as the complement of that on "Air in which a Candle has burned out," and is no less valuable.

"That candles will burn only a certain time in a given quantity of air
is a fact not better known than it is that animals can live only a
certain time in it; but the cause of the death of the animal is not
better known than that of the extinction of flame in the same
circumstances; and when once any quantity of air has been rendered
noxious by animals breathing in it as long as they could, I do not
know that any methods have been discovered of rendering it fit for
breathing again. It is evident, however, that there must be some
provision in Nature for this purpose, as well as for that of rendering
the air fit for sustaining flame; for without it the whole mass of the
atmosphere would, in time, become unfit for the purpose of animal
life; and yet there is no reason to think that it is, at present, at
all less fit for respiration than it has ever been. I flatter myself,
however, that I have hit upon two of the methods employed by Nature
for this great purpose. How many others there may be I cannot tell."

One of these methods he eventually finds to be, as in the first case, the action of vegetation, and he proves by a number of decisive experiments

"that plants, instead of affecting the air in the same manner with
animal respiration, reverse the effects of breathing and tend to keep
the atmosphere sweet and wholesome when it is become noxious in
consequence of animals either living and breathing, or dying and
putrefying in it."

The other method he conceived to be the action of water, since he found that by vigorous agitation with water, air which breathing had rendered noxious could again be breathed for a further period.

"I do not think it improbable but that the agitation of the sea and
large lakes may be of some use for the purification of the atmosphere,
and the putrid matter contained in water may be imbibed by aquatic
plants, or be deposited in some other manner."

When a confined volume of common air is placed in contact with a mixture of iron filings and sulphur made into a paste with water, a certain portion of the air is imbibed by the paste. This fact was first observed by Hales. Priestley repeated the observation and found that about a fifth or rather more of the volume of the air was thus absorbed. He noted that the residual "air" was rather lighter than common air, it had no action on lime-water and was exceedingly noxious to animals, by which is meant that it could not be breathed by them. Priestley had thus prepared nitrogen, but he failed to recognise the individuality of this gas.

In his _Statical Essays_ Hales makes mention of an experiment in which common air and air generated from pyrites by spirit of nitre made a turbid red mixture, and in which part of the common air was absorbed. This phenomenon "particularly struck" Priestley, who, acting upon Cavendish's hint that the red appearance was probably dependent "upon the spirit of nitre only" and that the metals might answer as well as pyrites, proceeded to investigate the action of nitric acid upon a number of the metals, and as the result of his inquiries he succeeded in isolating the gas we now know as _nitric oxide_, but which he termed _nitrous air_.

"Though," he says, "I cannot say that I altogether like the term,
neither myself nor any of my friends, to whom I have applied for the
purpose, have been able to hit upon a better."

This paper exhibits Priestley at his best. In it he describes all the main properties of nitric oxide.

"One of the most conspicuous properties of this kind of air," he says,
"is the great diminution of any quantity of common air with which it
is mixed, attended with a turbid red, or deep orange colour, and a
considerable heat.... The diminution of a mixture of this and common
air is not an equal diminution of both the kinds, which is all that Dr
Hales could observe, but of about one fifth of the common air, and as
much of the nitrous air as is necessary to produce that effect; which,
as I have found by many trials, is about one half as much as the
original quantity of common air.

"I hardly know any experiment that is more adapted to amaze and
surprise than this is, which exhibits a quantity of air which, as it
were, devours a quantity of another kind of air half as large as
itself, and yet is so far from gaining any addition to its bulk that
it is considerably diminished by it....

"It is exceedingly remarkable that this effervescence and diminution,
occasioned by the mixture of nitrous air, is peculiar to common air,
or _air fit for respiration_, and, as far as I can judge from a great
number of observations, is at least very nearly, if not exactly, in
proportion to its fitness for this purpose; so that by this means the
goodness of air may be distinguished much more accurately than it can
be done by putting mice or any other animals to breathe in it.

"This was a most agreeable discovery to me, as I hope it may be a
useful one to the public; especially as from this time I had no
occasion for so large a stock of mice as I had been used to keep for
the purpose of these experiments."

Priestley here suggests the basis of a method of _Eudiometry_, or method of measuring the goodness of air, which in his hands, but more especially in those of Cavendish, led to most important results. The quantitative analysis of the air may be said to have taken its rise from the publication of Priestley's paper.

In the course of subsequent work on nitrous air Priestley had occasion to study its action on iron, whereby he says:--

"A most remarkable and most unexpected change was made in the nitrous
air," the iron "makes it not only to admit a candle to burn in it, but
enables it to burn with an _enlarged flame_.... Sometimes I have
perceived the flame of the candle, in these circumstances, to be twice
as large as it is naturally, and sometimes not less than five or six
times larger; and yet without anything like an _explosion_, as in the
firing of the weakest inflammable air."

Priestley in this manner obtained _nitrous oxide_, the properties of which he subsequently studied in some detail.

In the paper which follows, _viz._, "On Air infected with the Fumes of Burning Charcoal," he incidentally gains further insight into the nature of atmospheric air. By what he called throwing the focus of a burning mirror on charcoal suspended in air contained in a glass tube standing over water or mercury--a favourite method of his when he had occasion to heat a substance in a gas--he could observe the phenomena with great precision. He noticed the formation of the fixed air and determined the degree of diminution when the burning took place over water or over lime-water.

"In this manner," he says, "I diminished a given quantity of air
one-fifth. Air thus diminished by the fumes of burning charcoal not
only extinguishes flame, but is in the highest degree noxious to
animals; it makes no effervescence with nitrous air, and is incapable
of being diminished any farther by the fumes of more charcoal.... All
my observations show that air which has once been fully diminished ...
is not only incapable of any further diminution ... but that it has
likewise acquired _new properties_, most remarkably different from
those which it had before...."

By heating pieces of lead and tin in air by means of a burning glass he observed the formation of a metallic calx, the volume of air was diminished, and it also "was in the highest degree noxious and made no effervescence with nitrous air."

The real significance of these phenomena was, however, wholly unperceived by Priestley, and phlogiston, as usual, led him astray. He had, of course, in all these experiments prepared _nitrogen_, and in a state of sensible purity. He imagined, however, that he had simply "phlogisticated" the air, the phlogiston coming from the charcoal and the metals, and that this phlogisticated air was imbibed by the water.

An experiment described by Cavendish led Priestley to study the action of "Spirit of Salt" (hydrochloric acid) upon copper. As Cavendish had already stated, the gas so evolved "lost its electricity by coming into contact with water." By collecting the gas over mercury Priestley was able to study its properties more exactly. From certain anomalies in the experiments he says:--

"I concluded that this subtle air did not arise from the copper, but
from the spirit of salt; and presently making the experiment with the
acid only, without any copper, or metal of any kind, this air was
immediately produced in as great plenty as before; so that this
remarkable kind of air is, in fact, nothing more than the vapour, or
fumes of spirit of salt, which appear to be of such a nature that they
are not liable to be condensed by cold, like the vapour of water and
other fluids, and therefore may be very properly called an _acid air_,
or more restrictively the _marine acid air_."

The new gas discovered by Priestley we now call hydrogen chloride. Ordinary hydrochloric acid is simply an aqueous solution of it.

"Water impregnated with it makes the strongest spirit of salt that I
have seen, dissolving iron with the most rapidity.... Iron filings,
being admitted to this air, were dissolved by it pretty fast, half of
the air disappearing and the other half becoming inflammable air, not
absorbed by water. Putting chalk to it, fixed air was produced."

He subsequently found that the marine acid air was more conveniently made by the action of oil of vitriol upon common salt.

From the "miscellaneous observations" with which this section of the volume concludes, there can be little doubt that Priestley, without knowing it, had prepared oxygen gas from nitre as far back as 1771. The accounts he gives of the behaviour of the gas obtained by heating nitre in a gun-barrel plainly indicate this fact.

"A candle," he says, "not only burned but the flame was increased, and
something was heard like a hissing similar to the decrepitation of
nitre in an open fire." He also noted the effect of nitrous air upon
it and concludes that "this series of facts relating to air extracted
from nitre appear to me to be very extraordinary and important, and in
able hands may lead to considerable discoveries."

The second section of the volume deals with experiments and observations made in 1773 and the beginning of 1774, and opens with an account of the discovery of _ammonia gas_.

"After I had made the discovery of the _marine acid air_, which the
vapour of spirit of salt may properly enough be called ... it occurred
to me that by a process similar to that by which this _acid_ air is
expelled from the spirit of salt an _alkaline_ air might be expelled
from substances containing volatile alkali.

"Accordingly I procured some volatile spirit of sal ammoniac, and
having put it into a thin phial, and heated it with the flame of a
candle, I presently found that a great quantity of vapour was
discharged from it; and being received in a vessel of quicksilver,
standing in a basin of quicksilver, it continued in the form of a
transparent and permanent air, not at all condensed by cold; so that I
had the same opportunity of making experiments upon it as I had before
on the acid air, being in the same favourable circumstances....
Wanting, however, to procure this air in greater quantities, and this
method being rather expensive, it occurred to me that alkaline air
might probably be procured, with the most ease and convenience, from
the original materials, mixed in the same proportions that chemists
had found by experience to answer the best for the production of the
volatile spirit of sal ammoniac. Accordingly I mixed one-fourth of
pounded sal ammoniac with three-fourths of slaked lime; and filling a
phial with the mixture, I presently found it completely answered my
purpose. The heat of a candle expelled from this mixture a prodigious
quantity of alkaline air; and the same materials ... would serve me a
considerable time without changing...."

He next studied the properties of the alkaline air. He found, of course, it was readily soluble in water.

"Having satisfied myself with respect to the relation that alkaline
air bears to water, I was impatient to find what would be the
consequence of mixing this new air with the other kinds with which I
was acquainted before, and especially with _acid_ air; having a notion
that these two airs, being of opposite natures, might compose a
_neutral air_, and perhaps the very same thing with common air. But
the moment that these two kinds of air came into contact a beautiful
white cloud was formed, and presently filled the whole vessel in which
they were contained.... When the cloud was subsided there appeared to
be formed a solid _white salt_, which was found to be the common _sal
ammoniac_, or the marine acid united to the volatile alkali....

"_Fixed air_ admitted to alkaline air formed oblong and slender
crystals.... These crystals must be the same thing with the volatile
alkalis which chemists get in a solid form by the distillation of sal
ammoniac with fixed alkaline salts....

"Alkaline air, I was surprised to find, is slightly inflammable....

"That alkaline air is lighter than acid air is evident from the
appearances that attend the mixture, which are indeed very beautiful.
When acid air is introduced into a vessel containing alkaline air, the
white cloud which they form appears at the bottom only and ascends
gradually. But when the alkaline air is put to the acid the whole
becomes immediately cloudy quite to the top of the vessel."

Up to now Priestley had mainly confined himself to the narration of the new _facts_ which he had discovered, barely mentioning any _hypotheses_ that occurred to him.

"The reason why I was so much upon my guard in this respect was lest,
in consequence of attaching myself to any hypothesis too soon, the
success of my future inquiries might be obstructed. But subsequent
experiments having thrown great light upon the preceding ones, and
having confirmed the few conjectures I then advanced, I may now
venture to speak of my hypotheses with a little less diffidence.
Still, however, I shall be ready to relinquish any notions I may now
entertain if new facts should hereafter appear not to favour them."

In a paper on "Common Air Diminished and made Noxious by Various Processes" he attempts to apply the current doctrine of phlogiston to account for the various phenomena he has observed, and with what success may be inferred from his conclusion

"that in the precipitation of lime by breathing into lime-water, the
fixed air, which incorporates with lime, comes not from the lungs but
from the common air, decomposed by the phlogiston exhaled from them,
and discharged, after having been taken in with the aliment, and
having performed its function in the animal system."

Priestley's attempts at theorising brought little satisfaction to him or to his readers. Indeed he says:--

"I begin to be apprehensive lest, after being considered as a _dry
experimenter_, I should pass into the opposite character of a
_visionary theorist_.... In extenuation of my offence let it, however,
be considered that _theory and experiments_ necessarily go
hand-in-hand, every process being intended to ascertain some
particular _hypothesis_, which, in fact, is only a conjecture
concerning the circumstances or the cause of some natural operation;
consequently that the boldest and most original experimenters are
those who, giving free scope to their imaginations, admit the
combination of the most distant ideas; and that though many of these
associations of ideas will be wild and chimerical, yet that others
will have the chance of giving rise to the greatest and most capital
discoveries, such as very cautious, timid, sober and slow-thinking
people would never have come at.

"Sir Isaac Newton himself, notwithstanding the great advantage which
he derived from a habit of _patient thinking_, indulged bold and
eccentric thoughts, of which his queries at the end of his book of
Optics are a sufficient evidence. And a quick conception of distant
analogies, which is the great key to unlock the secrets of Nature, is
by no means incompatible with the spirit of _perseverance_ in
investigations calculated to ascertain and pursue those analogies."

After this _apologia_, Priestley gives the reins to his imagination, or rather he allows phlogiston to drive the halting, ambling thing for him, with the result that he utterly loses his way and is eventually landed into an impassable quagmire. It is not too much to say that not one of the "Queries, Speculations and Hints" with which the volume closes has stood the test of time.

The second volume, which made its appearance towards the end of 1775, is dedicated to Sir John Pringle, at that time President of the Royal Society. It opens, as usual, with a somewhat prolix but characteristic preface. But to his biographer Priestley's prefaces are not the least interesting or valuable of his literary productions.

"In a preface," he says, "authors have always claimed a right of
saying whatever they pleased concerning themselves, and not to lose
this right it must now and then be exercised."

In this respect Priestley has championed the prerogatives of authors for all time. This particular preface begins with an expression of self-laudation for the little delay the writer made in putting the first volume to the press.

"In consequence of this considerable discoveries have been made by
people of distant nations; and this branch of science, of which
nothing, in a manner, was known till very lately, indeed now bids fair
to be farther advanced than any other in the whole compass of natural
philosophy.... And it will not now be thought very assuming to say
that by working in a tub of water or a basin of quicksilver we may
perhaps discover principles of more extensive influence than even that
of _gravity_ itself, the discovery of which, in its full extent,
contributed so much to immortalise the name of Newton.

"Having been the means of bringing so many champions into the field, I
shall, with peculiar pleasure, attend to all their achievements, in
order to prepare myself, as I promised in the preface to my last
volume, for writing the _history_ of the campaign."

After a delightfully _naïve_ compliment to his own ability as an accumulator of facts, and to his merits as an "instrument in the hands of Divine Providence ... concerning which I threw out some further hints in my former preface, which the excellent French translator was not permitted to insert in his version," he advances this testimony to his impartiality as an historian:--

"I even think that I may flatter myself so much, if it be any
flattery, as to say that there is not, in the whole compass of
philosophical writing, a history of experiments so truly _ingenuous_
as mine, and especially the section on the discovery of
dephlogisticated air, which I will venture to exhibit as a model of
the kind. I am not conscious to myself of having concealed the least
hint that was suggested to me by any person whatever, any kind of
assistance that has been given me, or any views or hypotheses by which
the experiments were directed, whether they were verified by the
result or not."

There is much else in the preface that might be quoted as illustrative of the character and mental attributes of its author. Priestley, the natural philosopher, never forgot that he was a minister of religion, and that to him theology was the greatest and most important of all the sciences, and he cannot forbear even, in what he intended to be a scientific disquisition on purely natural phenomena, from inculcating his belief in the divine origin of Christianity and his opinion concerning the doctrine of purgatory and the worship of the dead.

The first chapter is concerned with the discovery of what its author called _Vitriolic Acid Air_, but which we now know as sulphur dioxide.

Priestley imagined that as the liquid marine acid--that is hydrochloric acid--readily yielded an "air" on heating it might be that vitriolic acid, or oil of vitriol, would also afford a characteristic "air" when treated in a similar manner. Acting upon a suggestion of Mr Lane he heated oil of vitriol with olive oil, when he readily obtained a new species of air, which he collected over mercury as he "had been used to do it with the marine acid air; and the whole process was as pleasing and as elegant." Priestley at once surmised that the olive oil worked by transferring its phlogiston to the vitriolic acid, and he naturally concluded that any substance rich in phlogiston would bring about the same result. He next tried charcoal.

"I put some bits of charcoal into my phial instead of the oil or other
inflammable matter which I had used before, and applying the flame of
a candle I presently found that the vitriolic acid air was produced as
well as in the former process, and in several respects more
conveniently, the production of air being equable, whereby the
disagreeable effect of a sudden explosion is avoided.... Finding that
a great variety of substances containing phlogiston enabled the oil of
vitriol to throw out a permanent acid air, I had some suspicion that
mere _heat_ might do the same, but I did not find that there was any
foundation for that suspicion.... But though I got no air from the oil
of vitriol by this process, air was produced at the same time in a
manner that I little expected, and I paid pretty dearly for the
discovery it occasioned. Despairing to get any air from the longer
application of my candles, I withdrew them, but before I could
disengage the phial from the vessel of quicksilver a little of it
passed through the tube into the hot acid, when instantly it was all
filled with dense white fumes, a prodigious quantity of air was
generated, the tube through which it was transmitted was broken into
many pieces, and part of the hot acid being spilled upon my hand
burned it terribly, so that the effect of it is visible to this day.
The inside of the phial was coated with a white saline substance, and
the smell that issued from it was extremely suffocating.

"This accident taught me what I am surprised I should not have
suspected before, viz., that some _metals_ will part with their
phlogiston to hot oil of vitriol, and thereby convert it into a
permanent elastic air, producing the very same effect with oil,
charcoal, or any other inflammable substance.

"Not discouraged by the disagreeable accident above mentioned, the
next day I put a little _quicksilver_ into the phial with the ground
stopple and tube, along with the oil of vitriol, when, long before it
was boiling hot, air issued plentifully from it, and being received in
a vessel of quicksilver appeared to be genuine vitriolic acid air,
exactly like that which I had procured before, being readily imbibed
by water and extinguishing a candle in the same manner as the other
had done....

"After this I repeated the experiment with several other metals....
Copper treated in the same manner yielded air very freely, with about
the same degree of heat that quicksilver had required, and the air
continued to be generated with very little application of more heat."

The theory apart, this paper is as important as these on ammonia and the marine acid air, and exhibits Priestley at his best. The observations he makes concerning the main properties of the new gas and its solubility in water, its inability to burn and to support flame, its heaviness, its power to unite with ammonia, to be absorbed by charcoal and to liquefy camphor, are all accurate.

"Having hit upon a method of exhibiting some of the acids in the form
of air, nothing could be easier than to extend this process to the
rest."

Accordingly he attempted to procure what he called the _vegetable acid air_ by heating "exceedingly strong concentrated acid of vinegar," and states that he succeeded in obtaining an air which extinguished the flame of a candle and was soluble in water. The paper is very short and is full of contradictions. In reality, as he subsequently found, he was dealing with vinegar largely adulterated with oil of vitriol. The "vegetable acid air" had no real existence.

The next paper in the series is the most important of the whole, and the one of all others that has contributed most largely to Priestley's reputation. It is entitled "Of Dephlogisticated Air, and of the Constitution of the Atmosphere," and deals with the discovery of oxygen. It begins in the following characteristic fashion:--

"The contents of this section will furnish a very striking
illustration of the truth of a remark which I have more than once made
in my philosophical writings, and which can hardly be too often
repeated, as it tends greatly to encourage philosophical
investigations, viz., that more is owing to what we call
_chance_--that is, philosophically speaking, to the observation of
_events arising from unknown causes_ than to any proper _design_ or
preconceived _theory_ in this business. This does not appear in the
works of those who write _synthetically_ upon these subjects, but
would, I doubt not, appear very strikingly in those who are the most
celebrated for their philosophical acumen did they write
_analytically_ and ingenuously.

"For my own part, I will frankly acknowledge that at the commencement
of the experiments recited in this section I was so far from having
formed any hypothesis that led to the discoveries I made in pursuing
them that they would have appeared very improbable to me had I been
told of them; and when the decisive facts did at length obtrude
themselves upon my notice it was very slowly, and with great
hesitation, that I yielded to the evidence of my senses. And yet, when
I reconsider the matter, and compare my last discoveries relating to
the constitution of the atmosphere with the first, I see the closest
and the easiest connection in the world between them, so as to wonder
that I should not have been led immediately from the one to the other.
That this was not the case I attribute to the force of prejudice
which, unknown to ourselves, biases not only our _judgments_, properly
so called, but even the perceptions of our senses; for we may take a
maxim so strongly for granted that the plainest evidence of sense will
not entirely change, and often hardly modify, our persuasions; and the
more ingenious a man is, the more effectually he is entangled in his
errors, his ingenuity only helping him to deceive himself by evading
the force of truth."

He then points out that there are few maxims in philosophy that have laid firmer hold upon the mind than that air, meaning atmospherical air ... is a _simple elementary substance_, indestructible and unalterable, at least as much so as water was supposed to be. Priestley, in the course of his inquiries, was soon satisfied that atmospherical air was not an unalterable thing; that bodies burning in it, and animals breathing it and various other chemical processes, so far alter and deprive it as to render it altogether unfit for the purposes to which it is subservient; and he had discovered methods, particularly the process of vegetation, which tended to restore it to its original purity.

"But," he says, "I own I had no idea of the possibility of going any
further in this way and thereby procuring air purer than the best
common air."

As this paper is one of the classics of chemistry, as well as the chief corner-stone in the monument which Priestley erected to himself, it is necessary to examine it, as well as certain other papers which grew immediately out of it, in some degree of detail.

After a reference to a hypothesis of the origin and constitution of the atmosphere which occurs among the "Queries, Speculations and Hints" above referred to, and which is on a par with much in Priestley's speculations, he proceeds to relate the circumstances which more immediately led to the most important of all his discoveries. It was the accident of possessing a burning lens of "considerable force," for want of which he could not possibly make many of the experiments that he had projected.

"But having afterwards 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, putting them into
vessels [short, wide, round-bottomed phials], which I filled with
quicksilver and kept inverted in a basin of the same. Mr Warltire, a
good chemist, and lecturer in Natural Philosophy, happening to be at
that time in Calne, I explained my views to him, and was furnished by
him with many substances, which I could not otherwise have procured.