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Characters involved in the Phosphorus Story
Hennig Brand (1630 - c. 1710)
Transcripts of Publications (1677 - 1853)
Aerial Noctiluca : Robert Boyle 1680
Henry Oldenburg (c.1619 - 1677)
Georg Kaspar Kirchmaier (1635-1700)
Etching by John Evelyn dedicated
Sir Robert Southwell (1635-1702)
Johann Sigismund Elsholtz (1623 - 1688)
Christiaan Huygens (1629-1695)
HISTORY OF SCIENCE AND TECHNOLOGY
An Introduction to the Discovery of Phosphorus, a Chronology and a description of the different kinds of Phosphori.
The 17th century saw the beginning of the transition from alchemy to chemistry (sometimes referred to as chymistry). However, this change did not happen overnight and even Robert Boyle, often referred to as the Father of Modern Chemistry, had a lifetime fascination with alchemy. Many of the other members of the Royal Society were equally ready to take an interest in any news regarding alchemists. Alchemists were very secretive about their activities. They basically worked towards two goals - the discovery of the legendary and elusive Philosopher's Stone (which, among many other abilities, was said to have the power to endow everlasting life) and, no doubt by virtue of the Philosopher's Stone, the ability to perform transmutation, being able to change base metals into gold. Robert Hooke's minutes of the Royal Society meetings show that it's members spent much time discussing reports about individuals who had been blessed (somewhat incredulously) with astounding longevity.
The Royal Society was also intrigued by luminescence. The word luminescence was not used very much in the 17th century so anything showing luminescence, whether animal, vegetable or mineral, was referred to as a phosphorus (plural phosphori or phosphoruses), from the Greek meaning 'bearer of light'. Any report about a substance that emitted light without liberating heat was fervently debated during meetings and the members were always keen to obtain samples of these phosphoruses. Hooke's minutes reveal that animal and vegetable luminescence were frequent discussion topics.
The focus on phosphoruses from living sources had an arcanum base. The minutes of the Royal Society meeting on February 8th 1682 report a debate on the flammae vitae (the flame of life). The belief that the phosphorus from urine contained some of this flammae vitae explains why Johann Kunckel's 'phosphorus' pills, advertised as being a cure for almost any ailment, were extremely popular. There was nothing new in using urine as an ingredient in alchemical experiments - it had long been the source of ammonium chloride, also known as Spirit of Urine, which was able to dissolve copper.
Phosphorus as an element was identified by Antoine Lavoisier in 1777. Following the phosphorus story from 1669 through to 1685 introduces a list of characters (see left) whose roles in the tale are detailed through the links provided. The other links lead to letters, Royal Society minutes and publications from the period and a century later.
The information on the left attempts to give a description of the different types of phosphoruses that were investigated in the 17th century and a timeline of the main events.
1669 Hennig Brand, an alchemist living in Hamburg, produces phosphorus as the product of a complex distillation of urine. He names his discovery 'kalte feuer' (cold fire). Brand probably believed that he has isolated the elusive Philosopher's Stone. He keeps his 'recipe' secret for six or seven years during which time he tries, in vain, to achieve transmutation (making gold from another metal).
1674 Christoph Adolph Balduin, a member of the German Imperial Academy of Sciences, accidentally produces a phosphorescent stone after chemical treatment. He names his preparation Phosphorus Hermeticus or, alternatively, Magnes Luminaris, because it 'attracted light as a magnet attracts particles'.
1675 Christoph Adolph Balduin publishes a paper describing his 'phosphorus' but he omits the method he used to obtain it.
1675 Henning Brand, now short of money, makes his discovery public. Johann Kunckel (also spelt Kunckell), an alchemist and a professor from the University of Wittenberg travels to Hamburg to meet Brand. He fails to make a deal with Brand for either his supply of phosphorus or the recipe. Kunckel turns to Johann Daniel Krafft, a commercial agent from Dresden, to intervene with Brand on his behalf.
1676 Johann Daniel Krafft (also spelt Kraft, Craft or Crafft) travels to Hamburg. He double-crosses Kunckel and makes a contract with Brand. The contract specifies that all the phosphorus produced by Brand is given to Krafft. However, Brand does not give his recipe to Krafft.
Krafft begins his very successful and lucrative tour of European courts exhibiting das kalte feuer. He even boasted to those who attended his demonstrations that he was the discoverer, and we know of this from the writings of Johann Elsholtz, who was invited to the display put on for the Elector of Brandenburg on the evening of 24th April 1676. Elsholtz came away from the event believing that Krafft was the discoverer of phosphorus and wrote as much when he published an account of what he had witnessed in a philosophical journal.
1676 Kunckel is furious that Krafft has double-crossed him. He returns to Hamburg to see Brand. Brand still refuses to give Kunckel his 'recipe' but he does indicate to him that urine is used in the preparation.
July 1676 having received the hint about urine from Brand, Kunckel experiments with urine and succeeds in producing his own phosphorus. By April 1676 Kunckel manages to produce an impure sample. He perfects his technique and, by July 1676, he has produced a sample to match that of Brand's.
1676 Christoph Adolph Balduin sent a sample of his 'phosphorus' to the Royal Society in London and it is received by the secretary, Henry Oldenburg.
1676/1677 Kunckel spends a short time exhibiting his phosphorus at two European courts. He makes his money selling phosphorus pills.
1676 Georg Kaspar Kirchmaier a colleague of Kunckel's at Wittenberg University, publishes a paper entitled 'Noctiluca constans et per vices fulgurans' (Wittenberg, 1676) that describes Johann Kunkel's process for obtaining phosphorus.
1676/1677 Henry Oldenburg came across the paper by the German chemist Georg Kaspar Kirchmaier of a 'Phosphorus Fulgurans' that shone without first needing to be heated or exposed to sunlight. A small piece of this phosphorus was said to be still be shining after two years1 . The paper suggested that 'if a considerably big piece were prepared of it, it would serve for a perpetual, or at least a very long lasting light'.
1This has to be an exaggeration! It had probably been less than a year since it was made.
4th January 1677 the 'phosphorus hermeticus' sample sent by Christoph Adolph Balduin was examined and found to be phosphorescent. Christoph Adolph Balduin was elected as a member of the Royal Society.
25th February 1677 and 25th March 1677. Continuing the publicity campaign, Kirchmaier writes two letters to Henry Oldenburg, the Secretary of the Royal Society in London.
26th March 1677 Robert Boyle's 'An Account of four Sorts of Factitious Shining Substances' is published in Philosophical Transactions No. 135 Page 87.
March 1677 issue of Philosophical Transactions Oldenburg wrote a brief account which included the reports he had received from his foreign correspondents. Phosphorus smaragdinus, he wrote, "collects its light not so much from the Sun-beams, or the illuminated Air, as from the Fire itself."
1677 Krafft demonstrates his phosphorus at the court of Duke Johann Frederick of Saxony in Hanover and his friend Gottfried Wilhelm Leibniz is in the audience.
1677 Leibniz visits Brand in Hamburg. By this time Brand no longer supplying Krafft and is in need of money. Leibniz begins negotiations for Brand to take up the position of court alchemist in Hanover.
1677 Royal Society learns of a much brighter phosphorus from a letter sent from Germany to Robert Hooke, the Secretary of the Society, which described Kunckel's phosphorus.
1677 Leibniz writes to the Royal Society about the new phosphorus.
2nd August 1677 - Leibniz published 'Le phosphore de M. Krafft, ou liqueur de terre seiche de sa composition qui jettent continuellement de grands éclats de lumière' in Le Journal des Savants.
1677 Krafft invited to London by King Charles II (for a fee equivalent to £50000 in today's money).
5th September 1677 Henry Oldenburg died. Robert Hooke takes over as secretary of the Royal Society.
15th September 1677 Krafft is in London - visits Boyle's sister's house and there is a gathering of members of the Royal Society. (Hooke makes no mention of this in his diary for this day so it is possible that he had not been invited). Boyle writes a report on this visit that gets published in the Philosophical Transactions (Boyle refers to Krafft as "the Artist").
22nd September 1677 Krafft returns to Boyle's sister's house - Hooke is there (mentioned in his diary) - this visit was to show phosphorus igniting gunpowder (it had not 'worked' the week before - he had tried twice). - 'Krafft attempted (third time) to fire heated gunpowder with his phosphorus - he was successful with a small amount.' Returned with a piece of phosphorus the size of a pinhead. Krafft would not leave any of his sample. But he did tell Boyle it "somewhat belonged to the body of a man". Boyle thought this must be urine but did not follow up for about a year.
4th Jan 1678 - Baldwin's 'phosphorus' presented to the Royal Society and 'tried'. 11th January - experiments with Baldwin's phosphorus tried again without success.
14th March 1678 Royal Society Meeting - Dr. William Croon produced a phosphorus the same (as) that of Baldwinus which he affirmed was made here in England by an Englishman and was altogether as good as that produced by Mr. Baldwin himself. Mr. Hooke affirmed that he had another of the same kind and that .... had observed it. .... Appeared white if it were exposed to the light in the evening when the sun was almost ready to set.
21st March 1678 Royal Society Meeting - discussion about phosphorus baldwinus concerning which it was affirmed that the same was now made in England as good as that which was brought beyond (the) sea and it was desired that one of them might be procured to be examined at this society at their next meeting which Mr. Hooke said he would endeavour (to do so).
July 1678 Leibniz goes to Hamburg with a contract between Duke Johann Friedrich and Brand.
1678 Johann Joachim Becher, acting on behalf of his employer, Duke Gustav Adolph, tried to negotiate for Brand's recipe but Leibniz stopped him from doing so. Becher is diverted to Holland.
1678 Brand travels to Hanover. Leibniz is present when he makes phosphorus but Brand returns to Hamburg. After a few months Brand returns to Hanover a second time (as court alchemist) makes phosphorus there again. Once again, Brand returns to Hamburg.
1678 Johann Kunckel's "Oeffentliche Zuschrifft von dem phosphoro mirabili" (Leipzig, 1678). He publishes a paper but omits to give his 'recipe'. Kunkel designated his product 'noctiluca' and 'phosphorus mirabilis'.
1678/1679 Leibniz published Brand's recipe but under his own name - he did not credit Hennig Brand for his contribution.
1678 Boyle began his attempt to make phosphorus, he was working with Dr. Frederick Slare and one of his chemical assistants was a certain Mr. Daniel Bilger who had been in Boyle's employ for at least two years.
1679 Leibniz writes to Christiaan Huygens, sending him a sample of solid phosphorus (that has been placed in a bladder and sealed with wax for safety). Leibniz clearly states that "I can let you have more, since I can make it". Leibniz is keen to be accepted into the Académie de Sciences and offers to 'communicate its composition' if it is required.
1679 Wilhelm Homberg obtained the formula for making phosphorus from Johann Kunckel (they traded 'secret' information). It is possible that Homberg then traded this information with Robert Boyle.
10th April 1679 Royal Society Meeting - Mr. Thomas Henshaw gave an account of some trials he had made with the phosphorus presented by Mr. Slare one of which was that he found the same would receive a very brisk light from the evening light of the air but a very dusky one from that of a candle and none from the light of the moon. Desired that he would try to increase the light of the moon by a burning glass to see whether it would produce any considerable effects.
1679 Ambrose Godfrey Hanckwitz is only nineteen when he came to London as a chemical assistant. Seems to have been employed by Boyle in 1679 (there is evidence that this was his second job since moving to England).
3rd April 1679 Frederick Slare presented the Royal Society with a phosphorus of his own making.
1680 Hanckwitz had devised a method to produce a high yield of phosphorus. Godfrey made two forms of phosphorus for Boyle, liquid and solid (the liquid was impure - included 'oil of urine').
22nd January 1680 Royal Society Meeting Mr. Hooke produced a phosphorus given to him by Dr. Slare which was examined by Mr. Henshaw, Sir Cyril Wyche and several others, and it was found to be very receptive of light.
18th March 1680 Royal Society Meeting A letter in Latin from John Christopher Sturmius to Mr. Hooke dated 10 Feb 1680 was read ..... concerning the new phosphorus or shining pills etc. Dr. Gale was desired to return him thanks of the Society and to desire him to send some of those pills etc.
1st April 1680 Royal Society Meeting Mr. Henshaw read part of a letter from Sir Peter Wyche in which he desired to be informed whether Krafft who had been in England some time before, in order to sell his recipe of the phosphorus fulgurans, had received any reward for it. Several members were of the opinion that he had not received any at all.
8th July 1680 Royal Society Meeting Mr. Hooke gave an account to the society of a letter he had received from Monsieur Henri Justel in France (Paris 13 June 1680), in which the following information was worth mentioning ..... that they had with them in Paris a man who pretended to have 'the phosphorus' in a purer form than any yet produced. It was put into a well-stoppered glass and enlightened the whole room. A friend of his who saw it said that it outdid that (the phosphorus) of Kunckel.
30th September 1680 A paper (an account of his making phosphorus) written on 30th Sept of the Honourable Robert Boyle is deposited with the Secretary of the Royal Society on 14th October 1680 - not to be opened until his death (it was published in the Philosophical Transactions on 1st Jan 1693).
9th Dec 1680 Royal Society Meeting Very few of the Society met so there was nothing read. Only Mr. Hooke brought a book, published and presented by Mr. Boyle, called the "Aerial Noctiluca or Some New Phenomena and a Process of a Factitious Self-Shinning Substance".
16th Dec 1680 Royal Society Meeting Mr. Boyle's book on the Noctiluca that was presented last Thursday was produced and some sections were read and discussed. The members asked that thanks be sent to him (Boyle) for his gift.
12th Jan 1681 Royal Society Meeting Mr. Hooke produced a letter from Mr. Justel dated Paris 1 January 1681 ..... That Kunckell who invented liquid phosphorus had left Saxony and was gone for Poland.
Feb 1681 Hooke's minutes Royal Society mention Boyle's "book of the phosphorus".
1st Feb 1681 Royal Society Meeting Dr. Slare gave account of experiments with phosphorus. Mr. Hooke - letter from Mr. Theodore Haak, Berlin - Dr. Johann Sigismund Elsholtz hoped that he would soon have 'perpetual noctiluca' to enlighten a whole room.
9th Feb 1681 Royal Society Meeting Sir Robert Southwell showed a white powder made of 'Lapis Smaragdinus', only finely ground without any other preparation, which was spread on a copper plate. The plate was laid over a chaffing dish of coals until it was quite warm. In a dark room. The powder shone like a glow worm and continued to do so for some time. By degrees, the light diminished and disappeared. This was tried and it was remarked that if the plate was taken off of the coals, the powder still shone but, as the plate grew cold the light (from the powder) would diminish. When the plate was placed on the heat again the powder shone as before. It was observed that sprinkling water on the plate put out the light from the powder that became wet.
Sir Robert also showed the true recipe for making the phosphorus of Mr. Kunckel (which is the same as that which Mr. Krafft showed both in England and several other places). The phenomena had been described by the Honorable Mr. Boyle in one of the Philosophical collections. He (Sir Robert) did not have any of the substance with him but he promised to produce some for a future meeting of the Society.
He also gave a further account concerning the Phosphorus of Brand, which he called Brande Brand because it was first invented by Dr. Brand although now owned by Kunckelius & Krafft. He said that Dr. Brand had affirmed to him2 that he knew how to prepare a shining substance (as well) out of vegetable, animal or mineral substances, as well as out of wine, urine and mercury. However, he (Sir Robert) had not discovered the several ways and methods he (Brand) used to make them .
2This information is very interesting since it would seem to indicate that Sir Robert Southwell had direct contact with Hennig Brand, either in person or by letter.
23rd February 1681 Royal Society Meeting Upon the occasion of discussing the phosphoruses produced before by Sir Robert Southwell, Dr. Crone related some of his own observations about how a clean shirt shone when put on a very warm (surface) and rubbed with his hand - he had tried this often and he had never found it to fail.
23rd March 1681 Royal Society Meeting Sir Robert had delivered to the Society, as promised, a quantity of phosphorus, now presented by Mr. Hooke. This was the phosphorus from Dr. Kunckel which was made from the recipe that Sir Robert presented to the Society during a previous meeting. A glass container had been prepared for it (as asked for during the last meeting). The sample was examined and after many trials it was found to be much the same as the sample Mr. Krafft showed Mr. Boyle and several other persons some years earlier. However, it was remarkable that it needed a small quantity of fresh air to make it shine. Beside this, shaking it, agitating it and heating it produced a perfect flame and a kind of smoke but it had no manner of sensible heat.
4th August 1681 from the diary of John Evelyn Went to the Royal Society where was produced by Dr. Slaer (Slare) (one of the members) and extraordinary experiment ......
7th Dec 1681 Royal Society Meeting Dr. Slare produced a small piece of (his) solid phosphorus and he used it to write on a piece of paper. The writing was not visible when the candles were in the room but, when the candles were removed, the words shone very brightly and vividly, and were very legible. When the candles were brought back into the room the Dr. warmed the paper by the fire and all the letters appeared in a dark brown colour and very legible.
10th Dec 1681 Philosophical Transactions No 3 Dr. Frederick Slare "An account of several experiments made with the shining substance of the liquid and solid phosphorus".
21st Dec 1681 Royal Society Meeting Mr. Haak showed two sheets, and a draft belonging to them, 'De phosphoris observationis' written by Dr. Elsholtz of Berlin. These sheets contained a description of several sorts of phosphori known to Dr. Elsholtz and their effects.
Of the phosphorus Bononiensis
Of the phosphorus Liquidus
1682 The mathematician Ehrenfried Walter von Tschirnhaus was made a member of the Acadeémie Royale des Sciences for providing a recipe for making white phosphorus (obtained from his friend Gottfried Wilhelm Leibniz in exchange for the secret of two other chemical processes).
4th Jan 1682 Royal Society Meeting Upon the mention of the phosphorus, the president moved that a quantity thereof might be procured in order to carry out several other experiments, with more curiosity, in order to determine the true nature of the flame - what affinity it has with other flames, what effect the presence or absence of air has - what is the cause and how might the effects be increased and decreased etc..
Dr. Slare said that he had put a piece of phosphorus in a ring under a red stone.
Mr. Thomas Henshaw talked of an experiment that he had witnessed - in order to make an artificial carbuncle and that, one in place, it had continued to shine for three days.
8th Feb 1682 Royal Society Meeting From further discussion concerning the phosphorus there were several disagreements as to whether there was any such thing as 'flammula vitae'. Some thought that the experiments with phosphorus plainly proved such a 'flammula', extracted either immediately out of blood or out of urine. Mr. Hooke was of the opinion that it was impossible to prove. Although a shining and burning substance could be extracted from it (presumably blood and/or urine) it was possibly that the same substance might be able to be extracted from inorganic sources. This was proved by other shining substances (presumably from inorganic origin), particularly Lye. (This had been formally mentioned by the President - it (presumably Lye) had been made to shine by the strength of the fire).
22nd Feb 1682 Royal Society Meeting Some experiments with phosphorus were shown by Dr. Slare. Some pieces of the shining phosphorus shone much more than others (exact words 'exalted to a much greater perfection') with which the Society were very well pleased, especially Lord Alisbury, Lord Cavendish and Monsieur Justel who had 'not seen the like'.
15th March 1682 Royal Society Meeting Dr. Slare, for the entertainment of the strangers, showed some experiments with his phosphorus that he had previously shown to the society.
24th May 1682 Royal Society Meeting Dr. Slare brought a letter in Latin to himself from Dr. Elsholz dated 30 April 1682, which was read.... In this letter Dr. Elsholz mentioned his observations lately made about phosphorus fulgurous; and queried whether the serum of the blood, cow's milk or man's spittle might not by inspissation be brought to produce phosphorus as well as urine.
14th June 1682 Royal Society Meeting A Book of the Icy Noctiluca presented from the Author Mr Boyle was presented and it was requested that thanks be returned him, & the book put in the Library.
1683 Royal Society Meeting Slare's demo to Royal Society produced flashes of light from phosphorus mixed with oil of vitriol was "not a little surprising" but was "to the great pleasure of many inquisitive observers".
1683 Slare publishes "An Account of Some Experiments Made at Several Meetings of the Royal Society" by the Ingenious Fred. Slare M. D. Fellow of the Royal Society, and One of the College of Physicians in Philosophical Transactions.
1683 Hanckwitz stopped working for Boyle - This was the year his first son was born - named Boyle Godfrey (now using Godfrey as the family name). Set up business as manufacturing, analytical and consulting chemist. Eventually moved to Maiden Lane in Covent Garden. Started the first lab for the manufacture of phosphorus - The "Golden Pheonix".
1683 The French chemist and apothecary Nicholas Lemery also saw a demonstration by Krafft, probably in Paris, and he too said in his textbook of 1683, "Cours de Chymie", that Krafft was the discoverer. Lemery had been particularly flattered when Krafft gave him a little of the new material and he even managed to cause an accident with it.
1685 Godfrey had a prosperous business selling phosphorus - Even started exporting to Europe!
1685 Evelyn attends a demonstration by Slare at Pepy's house "Dining at Mr. Pepys's, Dr. Slayer showed us an experiment of a wonderful nature....."
1691 Wilhelm Homberg joined the Académie Royale in Paris and brought with him a recipe for the successful preparation of white phosphorus.
1694 Robert Boyle died in December 1693. His account of making phosphorus is published the following year (deposited 1680 with the Royal Society)
1708 Dr. Samuel Wall publishes "Experiments of the Luminous Qualities of Amber, Diamonds, and Gum Lac" that includes a history of his early work on phosphorus with Robert Boyle.
1737 A (unnamed) foreigner arrived in France and claimed the reward offered by the Académie des Science for a formula to make phosphorus. Jean Hellot was a witness to the successful trial that was made in the Jardin des Plantes. He write an account of the trial in the Memoires of the Académie in 1738.
1768 Carl Wilhelm Scheele and Johan Gottlieb Gahn discover phosphate in bone and develop a method to extract phosphorus from bone.
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