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Chemistry Index

Chemical Element Identification Timeline
History of Phosphorus : Introduction and Timeline

History of Science and Technology Index

Characters involved in the Phosphorus Story

Hennig Brand (1630 - c. 1710)
Johann Kunckel (1630 - 1703)
Johann Daniel Krafft (1624 - 1697) and Gottfried Wilhelm Leibniz (1646 - 1716)
Johann Joachim Becher (1635 - c. 1682)
Robert Boyle (1627 - 1691) and his Assistants

Transcripts of Publications (1677 - 1853)

Icy Noctiluca : Robert Boyle 1682

An Account of four sorts of factitious
Shining Substances : Robert Boyle 1677


A Paper of the Honourable Robert Boyle's,
Opened Since His Death (1692)


Some Observations made upon an Artificial
Shining Substance : Robert Boyle 1677


Extracts from John Evelyn's Diary 1681 and 1685

Experiments made with the liquid and of the solid
Phosphorus : Frederick Slare 1681


Extract from Experiments of the Luminous
Qualities of Amber : Samuel Wall 1708


On the Discovery of Phosphorus and a
Biography of Ambrose Godfrey
Hanckwitz : Joseph Ince 1853


An Extract from "An Account of some
Experiments upon the Phosphorus Urinæ"
by Ambrose Godfrey Hanckwitz 1731

Other Information

The Chemical Equations involved in the Luminescence of Phosphorus

 

The Aerial Noctiluca: or Some New Phenomena, and a Process of a Factitious Self-shining Substance.

Imparted in a Letter to a Friend, living in the Country.

By the Honourable ROBERT BOYLE, Fellow of the ROYAL SOCIETY.

LONDON.

Printed by Tho. Snowden, and are to be sold by Nath. Ranew. Bookseller in St. Paul's Church-Yard. 1680.

AN ADVERTISEMENT OF THE Publisher to the Reader.

The honorable author of the following papers, thinking it probable that the processes delivered in them, having hitherto been published by no man, will, as well for that reason, as for the nobleness of the subject, prove not unwelcome to the curious, in divers countries, where English is not understood: He was very willing, for their sakes, that this tract should be turned into Latin. And now, to prevent the needless pains of any, that may have a mind to make such a version, without having the opportunity to consult the author, upon any doubt of his meaning, I think fit to give notice, that the translation is, by the author's consent, made already, and, God permitting, will quickly appear in public.

Perhaps it will not be improper to add, that the reason, why the following English tract is printed in octavo, (as they speak) is, that it may be conveniently bound up, either with the notes, already published in the same form about divers particular qualities, or with those other notes that yet remain to be published about other qualities; to whose number light and inflammability may be referred.

The ensuing discourse having been written to a virtuoso1 living in the country, who has been for many years absent from London, it was thought fit in the beginning of these papers to give him some information about phosphoruses, and their several kinds in general, but it was not thought fit to publish at the beginning of the letter any thing of complement; since in that, neither the main subject, nor the reader, was concerned.

1Probably Dr. John Beale, Somerset

 

Robert Boyle

Robert Boyle

 

Footnotes

1Some researchers suggest that this visitor was Hanckwitz since he went by the name of Ambrose Godfrey when he resided in England. However, this is unlikely since Hanckwitz did not have a doctorate and Boyle clearly states that his visitor returned home soon after. Also, Hanckwitz was young and only a laboratory assistant and, as such, unlikely to have had the private audience with Boyle that this letter suggests.

2Laboratory Assistant - Boyle was probably referring to Daniel Bilger, assuming this experiment took place in 1678 or 1679. Ambrose Godfrey Hanckwitz may have started working for Boyle at this time and, if so, he would have been Bilger's assistant.

 

The Philosophical transactions of the Royal society 1665 -1800 were re-published in 1809 with comments by Charles Hutton, Richard Pearson and George Shaw.

The following are footnotes that the editors added.

P 489 Voll II : On the Variation of the Needle; and of the Phosphorus of Dr. Kunkel. By J. Chr. Sturmius. Philos. Collect. No. 2 p.8

Footnote: Among foreigners, Kunckel is entitled to the discovery (equally with Brandt) of preparing phosphorus from urine; but from the papers deposited by Mr Boyle with the secretaries of the Royal Society and opened after his death, it would appear that this indefatigable experimenter, our countryman, had found out the method of obtaining this curious product sometime before. The circumstance we shall barely mention here, postponing the further consideration of it until we come to that part of the Transactions containing Mr. Boyle's communication on this subject.

P478 Voll III: A Paper of the Hon. Robert Boyle, deposited with the Secretaries of the Royal Society, Oct. 14, 1680, and opened since his death; being an account of his making Phosphorus etc. No 196 p.583

At p.489, Vol.II of this abridgement, it has been mentioned in the biographical anecdotes concerning Kunckel, that Mr Boyle deposited with the secretaries of the Royal Society, some years before his death, an account of a process, whereby he succeeded in producing phosphorus from urine. This he did at a time (1680) when the processes of Brandt and Kunckel were not known, or if known were kept a profound secret. It is true that Mr. Boyle had previously seen some specimens of phosphorus, both solid and liquid, which had been brought to England by Kraaft; but this person was ignorant of chemistry; and all that Mr. Boyle could collect from him, was that the phosphorus which he exhibited was produced "somewhat that belonged to the human body". Mr. Boyle therefore appears to be entitled to the claim of having discovered a method of obtaining this curious product, equally with the German chemists, Brandt and Kunckel. Nor is this claim by any leans invalidated by the circumstance mentioned by Stahl; viz. that Kraaft told him he had communicated the process to Mr. Boyle; as Kraaft's general character, and in particular his treacherous conduct towards Kunckel, destroy the credit of such an assertion; and to this that Mr. Boyle's candour and probity stand too well attested, to leave the slightest suspicion that he would have concealed such a circumstance, had it been true. But to remove all doubt on this subject we shall insert the account of this transaction in Mr. Boyle's own words: "After Mr Kraaft had shown me (says this distinguished philosopher) both his liquid and consistent phosphorus ...."

 

 

 

HISTORY OF SCIENCE AND TECHNOLOGY

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The aerial noctiluca, or, Some new phenomena, and a process of a factitious self-shining substance imparted in a letter to a friend living in the country : Robert Boyle 1680

The full text of Aerial Noctiluca is available as a PDF through this link that opens in a new window.
The line numbers shown in the text below refer to the PDF.

Extracts from Aerial Noctiluca : Robert Boyle 1680 with notes

In Aerial Noctiluca, Boyle is publishing a letter he had written sometime earlier to Dr. John Beale who lived in Somerset. Boyle might have removed some detail prior to his article being published in Philosophical Transactions, particularly the name of his German visitor.

Boyle begins by describing two phosphorescent stones. He shows a slight frustration with Christoph Adolph Balduin for not having published his method of preparing the Phosphorus Hermeticus.

(Line 71) "The first of these consists of such bodies as shine only by the help of external illustration, or (if you please) such bodies, as being exposed to the beams of the sun, or those of a vigorous flame, will retain a lucidness, and continue to shine sometime in the dark. Of this kind is the Bolognian Stone, skillfully prepared; and of this sort also is the Phosphorus Hermeticus of Balduinus, of whose phenomena, but not the way of making it, the author has given the learned world an account."

Later in his text, Boyle is vague about his recent visitor from Italy. He had tried to get a sample of the Bolognian Stone to shine but had never succeeded (due to the need for copper impurities). The small, treated sample he possessed had long since ceased to shine.

(Line 81) "Bolognian Stone was for some years before grown very rare, even in its own country, Italy, which scarceness, an ingenious traveler, then lately come out of those parts, told me he imputed to the death of the person that used to prepare the stone at Bologna, without having left a sufficient account of his way of making it lucid."

(Line 107) "The Bolognian Stone, skillfully prepared, would retain its virtue of being excited for a much longer time: For I remember (whatever learned men have delivered to the contrary) I had a small piece of it, which, though I kept it negligently enough in an ordinary little wooden box, retained its virtue for several years after I had it, which was not till a great while after it was first prepared."

Boyle continues his letter by describing a new phosphorus that does not need a heat source to make it shine. He is unhappy with the name Noctiluca since it does not, in his opinion, distinguish the new phosphorus from those already known.

(Line 125) "..... a Noctiluca, which, though in strictness I cannot think it as proper a name as could be wished, since the other phosphorus will shine in the night as well as the day, if it be excited with the flame of a culinary fire, or of a large candle; yet since the name has been received by several, and since it is not easy in our language, to express the thing clearly in one word, I shall (though for brevity, as much as distinction's sake) admit the use of this name yet without forbearing sometimes to substitute for it that of a self-shining substance, which is more expressive of its nature."

Boyle follows this with an account of Johann Daniel Krafft's visit to the English court and his demonstration of the new Noctiluca.

(Line 137) "Of this substance, Mr. Daniel Krafft, a German chemist showed His Majesty two sorts or degrees.

To the first of which, I took the liberty to give the name of Consistent (or Gummous) Noctiluca, not in that sense, wherein the word is opposed to soft, for this substance was at least as yielding as bees' wax in Summer; but as the word consistent is employed as equivalent to firm, and opposed to liquid and fluid ........ it is called by some in Germany, The Constant Noctiluca; which title it does not ill deserve, since this phosphorus is much the noblest we have yet seen."

Boyle was disappointed about the quantity of the Constant Noctiluca that Krafft had with him since there was not enough, according to Krafft at least, to experiment on.

(Line 158) "..... Nor had the possessor enough of this substance to invite his consent to any trial to improve it, the quantity he had at London, scarce exceeding in bulk the kernel of an almond."

Next Boyle described the Liquid Noctiluca that Krafft had brought with him.

(Line 163) "Besides this Gummous Noctiluca, Mr. Krafft had a liquid one, that, perhaps, was made only by dissolution of the former in water, or some convenient liquor; but the lucidness of this, was not permanent like that of the other, as I have noted in another paper: but within no very long time, especially when it was divided into smaller portions, and left exposed to the air, would expire or vanish."

Boyle continues to tell his friend about his own discovery, Aerial Noctiluca.

(Line 176) "For this of ours would not shine of itself, like the Constant Noctiluca, nor yet in that manner that the Liquid Noctiluca did; but the bare contact of the air, without any external illustration or heat, would immediately produce a light, (which might easily be made to last a good while in a well stoppered vessel:) And, which is considerable, the substance that shined, was not the body of the liquor included in the vial, but an exhalation or effluvium mingled with the admitted air: for both which reasons, I gave it the name of Aerial Noctiluca".

Boyle then makes reference to a paper by Johann Sigismund Elsholtz that he has not yet read.

(Line 189) "..... because I have heard of a paper printed in Germany by an ingenious man, whose name (if I mistake not) is Elsholez, wherein particular mention is made, in an historical way, of the German Noctiluca: but this paper I cannot yet procure, and therefore you would do well to consult it, if you can get it; and I am not averse from thinking, that future industry may discover some new kinds or variations of self-shining substances, that will deserve new names, and among them, perhaps, that of solid Noctilucas."

Boyle then gave a brief history of the new phosphorus. He has heard vaguely of Hennig Brand but 'the word on the street' is that Johann Kunckel is the true discoverer.

(Line 206) "I find the first invention is by some ascribed to the above mentioned Mr. Krafft, (though I remember not, that when he was here, he plainly asserted it to himself;) by others, attributed to an ancient chemist, dwelling at Hamburg, whose name (if I mistake not) is Mr. Branc, and by others again, with great confidence, asserted to a famous German chemist in the Court of Saxony, called Kunckelius. But to which of these so noble an invention, as that of the two German Noctilucas, is justly due, I neither am qualified nor desirous to judge....."

Boyle relates the visits Krafft made to his sister's house in September 1677. He describes how he offered Krafft an exchange of information and, in return, obtained a tantalizing hint.

(Line 242) "...... I had lying by me, among my yet unpublished notes of the mechanical origin of divers qualities, a collection of some observations and thoughts concerning light and I was (also) the more encouraged to attempt somewhat this way, because having, at Mr. Krafft's desire, imparted to him somewhat that I discovered about uncommon mercuries, (which I had then communicated but to one person in the world) he, in requital, confessed to me at parting, that at least the principal matter of his phosphoruses, was somewhat that belonged to the body of man".

Boyle mused over Krafft's parting gift. One of the factors for the choice of urine as a starting block was that he already had a stock of it.

(Line 262) "...... there being divers parts of the human body, that have been taken to task by chemists; and, perhaps, by me as carefully, as by some others, my choice might have been distracted between the blood, the solid excrements, the bones, the urine, and the hair, of the human body; if various former trials and speculations upon more than one of those subjects, had not directed me to pitch upon that, which was fittest to be chosen, and of which, as I had formerly set down divers experiments and observations, so I had made provision of a quantity of it, and so far prepared it, that it wanted but little of being fit for my present purpose.

Boyle goes on to explain why he needed to set his investigation aside and how, when he did begin his experiments, he was put on the wrong track.

(Line 275) "........ before I had made any great progress in my design, I was by divers removes, indispositions of body, law-suits, and other avocations, so distracted, or at least diverted, that I laid aside the prosecution of the phosphorus for a long time. And when afterwards I resumed it, though I wrought upon the right matter, yet I was diverted from the right way, by a process that I received from beyond sea, as a great Arcanum, that would certainly produce the Noctiluca aspired to, for partly upon this account, but more, because I saw that the chief ingredient in this process, was that which I, with reason, took to be the best matter, I was induced to pursue the prescribed method for some months, but without success; the true matter being, as I concluded, too much either altered or clogged by the additional ingredients that were designed to improve it; besides, that the degree of fire, though a circumstance of the greatest moment, was overlooked, or not rightly prescribed."

It would seem that Boyle had received inaccurate information from the Continent. The reference to "the true matter being altered or clogged" would indicate that he may have mixed urine with solid waste. In terms of timing, Krafft's visit was in September 1677 and Boyle was 'diverted for a long time' and then wrongly directed 'for some months'. It is likely that the German visitor mentioned below turned up in 1679.

(Line 293) "However, adhering to the first choice I had made of a fit matter, I did not desist to work upon it by the ways I judged the most hopeful when a learned and ingenious stranger, (A. G. M. D.1 countryman, if I mistake not, to Mr. Krafft) who had newly made an excursion into England, to see the country, having, in a visit he was pleased to make me, occasionally discoursed, among other things, about the German Noctiluca, whereof he soon perceived I knew the true matter, and had wrought much upon it. He said something about the degree of fire that made me afterwards think, when I reflected on it, that that was the only thing I wanted to succeed in my endeavors. And there was the more reason to think so, because for want of a due management of the fire, we had divers times failed, of making the Phosphorus of Balduinus, not only after we had more than once wrought upon the right matter, but after we had actually made the Phosphorus."

It was not all smooth sailing at first but Boyle was determined that it should work:

(Line 311) "...... having yet some quantity of the matter in such readiness, that it needed but the fire to let me see what I ought to think of the hint the ingenious traveller had given me, I caused the trial to be renewed, which, proving unsuccessful, diminished much of my stock of prepared matter, but it did not so discourage me, as to hinder me from reiterating the attempt (without much varying it) with a good part of what remained. And though at this time also, all the care and diligence that could be employed, did not hinder an unlucky miscarriage, that kept the trial from being fully satisfactory; yet being confident upon the nature of the thing, I would not believe the skillful laborant2when he told me with trouble, that what I expected, was not at all produced: But going myself to the laboratory, I quickly found, that by the help of the air, or some agitation of what had passed into the receiver, I could, in a dark place (though it was then day) perceive some glimmerings of light, which, you will easily believe, I was not ill pleased to see."

The full text of Aerial Noctiluca is available as a PDF via the link at the top of the page. Exactly how much help Boyle received to improve his method is debatable. Aside from the hint from the German visitor about increasing the heat during the final distillation, it is possible that Boyle took part in an exchange of information with Wilhelm Homberg when he visited London in 1679. It is reported that Homberg had already made a similar intellectual exchange with Johann Kunckel earlier in the year. Homberg held a letter of introduction from Gottfried Leibniz to Boyle, and Leibniz had obtained the famous recipe from Hennig Brand. Frederick Slare, one of Boyle's collaborators at the time, was in communication with Leibniz so information could have been received via this route. However, Boyle could not have received any information from Krafft since Krafft was never in possession of this information.

The footnotes added by Hutton, Pearson and Shaw in 1809 to the Philosophical Transactions from the period are very interesting (see left). Robert Boyle's character is impeccable, it would seem! The authors do seem to have seen Krafft in the right light, however.

The exchange of new information was a bartering tool used by the scientists of the day. Boyle openly admits that he offered Krafft unpublished information "about uncommon mercuries" in exchange for more detail on how phosphorus was produced.

It is quite likely that information about the process was exchanged between Boyle, Homberg, Leibniz and Kunckel, either directly or indirectly, and it is unlikely that any of them really produced phosphorus independently of each other.

 

 

 

 

 

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