SYMHC Classics: Hennig Brand

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Speaker 1: Happy Saturday. This week we talked about Ricketts and vitamin D and we mentioned that in sixteen sixty nine, hennig Brand figured out what phosphorus was by boiling You're in a lot of it. We have a whole episode about that. It came out on April twenty ninth, twenty nineteen, and it is today's Saturday Classic. At the beginning of this classic, we talk about an event called Bawfest. It doesn't seem like there's been one of these in the past few years, but there are still some videos from earlier ones available on YouTube if you want to check them out. So enjoy. Welcome to Stuff You Missed in History Class a production of iHeartRadio. Hello, and welcome to the podcast. I'm Tracy V. Wilson and I'm Holly Frye. Every year, there's a thing in Cambridge, Massachusetts called Bahfest. It's held another but the wedding Cambridge on the MIT campus is the one that I go to. It's the Festival of bad ad hoc Hypotheses. It's a place where people present their scientific papers, except the scientific papers are fake and all so funny and very rare, well argued and sometimes really plausible. On top of being so hilarious. So like, for example, last time, the winning talk was all about the role of noise in the spread of bubonic plague in the fourteenth century, and it was accompanied by a whole lot of pictures from illuminated manuscripts. And I don't want to get into more detail than that, because they put videos of all these things online and I want anybody who goes to watch it to see all the hilarious reveals firsthand. It is often a very cool blending of science and history and fakery and hilarity altogether. And the reason I'm talking about this is that the winners of this very silly, nerdy thing used to get a three D printed representation of Darwin looking doubtful, but now they get a trophy of hennig Brand discovering phosphorus. Hennig Brand discovered phosphorus by boiling pea. So the first time I heard about this at Bohest, I was like, we gotta do a podcast on that. It has just taken me a few years to actually get to it. In case it was not clear, this episode is going to have a lot of your in in it. Hooray. I love a p joke They're very funny to me because I'm crass. One of my cousins has a daughter who's just at the age to be having sleepovers and at the age where mentioning of any bodily function is just instantly hilarious. And I remember as a kid, if somebody was like pee pee, it would just send everyone into giggles forever. Yeah, it was very different as a child, you know. I was raised with a lot of shame about your body and anything it might do or pretty until I became a little bit older and out in the world where I was like, you, guys, urine is really funny. But as a child, if you said something about p a sleepover, there would be mortification and like, oh no. A very different culture. Yeah, yeah, yeah, yeah, little Victorian at my house in that. Regard to the matter in hand, phosphorus is a chemical element, and if you need a quick chemistry refresher, elements are a basic building block of matter, and elements are made of atoms, and atoms are made of sub atomic particles, but you cannot take those subatomic particles out of an atom by ordinary chemical means. A pure piece of an element like phosphorus is made of phosphorus atoms, and one atom of phosphorus is the smallest piece of phosphorus that you can get. Yeah, I'll take one phosphorus please. When I wrote that, I made it almost sound like all elements are made of phosphorus. That's not It's that all elements are made of atoms of that type of elements. And so several chemical elements were known to the ancient world. You'll see slightly different lists depending on where you look, but in general, humans have known about gold, silver, copper, iron, lead, ten zinc, arsenic, antimony, mercury, sulfur, and carbon for thousands of years. Pretty much any ancient culture that has written records names at least some of these in those records. These elements have all been known about for so long that we could not really say who discovered them or who first concluded that there was anything special about them. Phosphorus, on the other hand, is the first element whose discoverer we can name, and that was hennig Brand in about sixteen sixty nine. But unlike most of the other elements we just listed, phosphorus doesn't exist in its pure elemental form out in the natural world. It's extremely reactive, so instead, it's found in phosphate compounds. Those compounds are used to produce elemental phosphorus, which is called white or yellow phosphorus. White phosphorus can then be used to make more stable allotropes, including red and black phosphorus. In casual use, the words phosphorus and phosphates are used almost interchangeably, sort of like how people say carbon to mean carbon dioxide. Phosphates are fundamentally necessary to life on Earth. They're part of the structure of DNA and RNA. They're also a component and a denizene triphosphate or ATP, which carries energy within all living cells. Calcium phosphate helps provide the strength in our bones and teeth, so I mean, it's just not an exaggeration to say that we would be dead without phosphorus. Are very squishy. People have also been intentionally using phosphorus for thousands of years before Brand discovered it, without knowing that that was what they were doing. In some parts of the world, the soil doesn't contain a lot of phosphorus, and even in places where the soil starts out phosphate rich, it loses its phosphates and other nutrients over times. Through farming. For as long as people have deliberately cultivated crops, they've also understood that there was something about the soil that needed to be replenished in order for crops to continue to thrive. There a lot of the strategies people have used to try to make their crops grow better have really been adding phosphorus, along with the other essential nutrients of nitrogen and potassium, back into the soil. As examples, the practice of burning off the stubble of last year's crop doesn't just clear the land for new planting. The ash also contains phosphorus, which goes back into the soil. People have also fertilized their crops with things like manure, urine fish, and oyster shells, all of which contain phosphorus and other nutrients. Crop rotation takes advantage of the differences in how different plants use nitrogen, potassium, and phosphorus to try to keep all three of those readily available in the soil. People did things like this for centuries without knowing what phosphorus was or that the crops that they were growing needed it. Ancient people's use of phosphorus also wasn't limited to agriculture. As one example, for thousands of years, people have used stale urine to clean things. A big reason for this is that urine contains urea, which decays into ammonia when it's left out for a long time. But urine also contains a lot of phosphates, and phosphates help make other cleaning agents more efficient. Please don't take this as any sort of household cleaning tip. When we were in San Francisco at the end of our tour last year, I went to the Bookbinders Museum and that I had a guided tour of the Bookbinders Museum, and one of the things that I learned about is how in one element or one part of the book binding printing process, there were these little ink daubers that were sort of leather covered things that you would daub in the ink and you would put that on the plate that you were going to print, and if that dried out, your apprentice had to go and clean them and start completely over. So part of the apprentice's job was to keep that nice and moist. And the tour guide said, do you have any ideas of what they might have used to clean these things? And I was like, I bet it's urine, because that was the thing that I could think of. It would be, you know, in the early days of bookbinding, would probably use to be clean to clean something, and she's specified that it was stale urine, and that is for the reason that we just said. So. Of course, when Hennebrand was alive, people did not know what phosphorus was or that it was connected to all of this, and even after he made his discovery, people didn't really understand what it was he had found. At the time, European scientists still understood the world in terms of not the chemical elements that we think about today, but the four elements of earth, air, fire, and water. The field of alchemy was just starting to evolve into the field of chemistry when he lived, and the definition of elements was just starting to evolve from those four elements into more like today's definition. And there's more about the shift from alchemy to chemistry in our most recent Saturday classic, but as it relates to hennig Brand. By the sixteen sixties, there were still a few alchemists searching for the fabled Philosopher's Stone, which was believed to turn base metals into gold and produce an elixir that could cure diseases in prolonged life, and Brand was one of them. Hennigbrand's discovery of phosphorus came about because he thought the secret to the Philosopher's Stone might be found in urine, and we'll get to why he thought that on how he made his discovery after a sponsor break. We do not know all that much about Hennig Brand as a person. Sometimes as is spelled Hennig instead of Hennig. Sometimes his last name is br a and T or brn d T instead of br and D. He was probably born in Hamburg and what's now Germany sometime around sixteen thirty. He seems to have spent some time as a low level army officer during the Thirty Years War, and that suggests that he was from a middle class family because he was an officer, so probably they were not very poor, but also he was not of a very high rank, so they probably weren't all that prominent either. In addition to his army service, Brand seems to have done at least part of an apprenticeship with a glass blower before turning his attention to alchemy. This would have given him the skills to make some of the glass vessels used in alchemy, and a glass blower's furnace would have been useful to his alchemical pursuits as well. At some point in all of this, he married a woman whose dowry was large enough to fund his research. After Brand's first wife died, he remarried a woman named Margaretta, who had also been married before. Her son became Brand's assistant in his workshop, and her family's money continued to pay for all of his experiments. He may have also presented himself as a physician, although according to a nineteenth century history of chemistry, he was quote an uncouth physician who knew not a word of Latin. As we said before the break, Brand was looking for the Philosopher's Stone, which was believed to turn base metals into gold and produce the elixir of life. Many alchemists believed that the key to the Philosopher's Stone was somewhere in human bodily fluids, and the fluid the Brand focused on was p Not only is urine a bodily fluid, but it is also yellow, you know, like gold to be clear. Bread was not the only person who thought that maybe urine had something to do with gold. Urine was pretty mysterious at the time. Nobody knew how the body produced it or why it was yellow, but they did know that it did all kinds of fascinating and seemingly magical things. We talked about. It uses a cleaning agent before the break, but it was also used in tanning leather and dying fabric, and in all kinds of alchemical recipes. Urine was also used in some methods of making saltpeter, and then the saltpeter was used to make gunpowder, so part of gunpowder was from urine. With all of those things going on, it wasn't really that much of a stretch for people to suspect that this strange, potent, seemingly slightly magical liquid might be yellow because it contained gold. Today, though, we know that the yellow color mostly comes from a substance called urobilin, which is one of the end products of the bodies breaking down the iron containing molecule. Heame brands experiments with urine involved boiling it over and over in a vessel called a retort. A retort is a spherical vessel with a long, downward pointing spout. If you heat up something in a retort. The vapor rises then condenses in that long spout, so you can use it to distill things. As Brand was distilling urine in his retort, the fluid dripping out of the spout started spontaneously bursting into flame. And it also smelled very strongly of garlic. And he found if he caught it in a vessel and then stoppered the vessel up, it would glow regardless of whether it had been exposed to any light. I'm sorry to laugh, Brand, it's funny, though. It's like my fiery garlic glopie. I don't The whole thing is very funny. Brand thought that he was onto something, perhaps even the Philosopher's stone, so he kept refining his process, producing this whitish waxy substance that was very volatile if exposed to air, and it had a bluish glow if it was kept away from air. Here is his recipe for making phosphorus, as published in Philosophical Experiments and Observations of the late eminent doctor Robert Hook, which was published in London in seventeen twenty six. Since this was almost sixty years after Brand's discovery and recorded by a different person, It is likely that various steps have been changed or added, but this definitely will give you a sense of what all was involved in this. So under the heading Phosphorose Elementaris by doctor Brandt of Hamburg, it reads quote, take a quantity of urine, not less for one experiment than fifty or sixty pails full. Let it lie steeping in one or more tubs or an hogshead of oaken wood, till it putrefy and breed worms, as it will do in fourteen or fifteen days. Then in a large kettle, let some of it boil on a strong fire, and as it consumes and evaporates, pour in more and so on, till at last the whole quantity be reduced to a paste, or rather a hard coal or crust, which it will resemble. And this may be done in two or three days, if the fire well tended, but else it may be doing a fortnight or more. So for one batch of phosphorus, brand was leaving urineo out in pails for about two weeks and then boiling it for between two and fourteen days, and that is not the end of the process. From there you powder the previously made coal or crust end quote, add there to some fair water about fifteen fingers high or four times as high as the powder, and boil them together for one quarter of an hour. Then strain the liquor and all through a woolen cloth. That which sticks behind may be thrown away, but the liquor that passes must be taken and boiled till it come to a salt, which will be in a few hours. This recipe continues on with adding more ingredients and steeping them together until the substance became sort of a pap which left behind a red or reddish salt after being evaporated in sand. And then that went into a retort and quote for the first hour began with a small fire, more the next, a greater, the third and the fourth, and then continue it as high as you can for twenty four hours, sometimes by the force of fire. Twelve hours proves enough for when you free the recipient white and shining with the fire, and there are no more flashes or as it were, blasts of wind coming from time to time from the retort, then the work is finished, and you may with a feather gather the fire together or scrape it off with a knife where it sticks. This recipe goes on to stress the need to preserve this fire in an airtight container, and how if you put it in the sun it might quote kindle gunpowder. I think that might just mean explode. Uh. This. This recipe also contains a cautionary tale quote. My author says he had once wrapped a knob in wax at Hanover, and it being in his pocket, and he busy near the fire, the very heat of it let inflame and burned all his clothes and his fingers also, for though he rubbed them in the dirt, nothing would quench it unless he had water. He was ill for fifteen days and the skin came off. So don't do that. We should note that it's possible that Paracelsus used a similar process to produce phosphorus. In the sixteenth century, more than one hundred years before Brand's discovery, he wrote about a process for repeatedly distilling urine, which would cause what he described as the earth, air, and water to rise while the fire fell out of it. After doing this several times, he said there would be quote congealed certain icicles, which are the element of fire. That sounds close enough to what Brand was doing that these icicles could have been phosphorus, but we also really don't know. It just merits mentioning as a potential comparative. Paracelsus has been on my episode list for a very long time, long enough that I was getting ready to do it, and then saw Bones did it, and I didn't want to feel like I was copying saw Bones, even though not everybody listens to both shows. But now it's been long enough, maybe he will creep farther up the list. There are also other accounts that describe Brand's process a little differently than that recipe that we just went through, and in one of them, the salts that are produced after the first round of distilling the urine are discarded. That is actually where most of the phosphorus would have been at that point in the process, So if Brand was doing it that way, he would have been throwing away most of what he was trying to get. Regardless, though this was a long, involved, complicated, and frankly gross process, a seventeen sixty seven Dictionary of Chemistry described it as more curious than useful, along with being quote both costly and embarrassing. But Brand was very fond of his costly embarrassing discovery. He named it cold fire or sometimes just my fire. It's not clear who was the first person to call it phosphorus, which is from Latin words that mean bringer of light or light bringer. That same term has also been used to describe a variety of other glowing substances. Brand kept his discovery secret for about six years, and we'll get to what happened when knowledge spread about it after we first have a little sponsor break. Henig Brand's discovery became public knowledge through a murky series of events involving two other men named Johann Kunkel and Johann Daniel Kraft, who, like a lot of other people in the story, worked in both chemistry and alchemy. It seems as though Kunkle had a piece of Bologna's Stone, and this was a rock that was first described in sixteen oh three by Vincenzo Casciolo, and this stone glowed in the dark. Casciolo was a shoemaker, and like so many other people, he was hoping to find gold. He had collected a bunch of interesting rocks from the mountains near his home in Bologna in what is now Italy, and he discovered that if you ba them and then left them out in the sun. They would glow in the dark. Bologna stone became a curiosity and a source of fascination, as people wondered whether there was something magical about it and whether it might have something to do with the Philosopher's Stone. Galileo described it this way in sixteen twelve quote, it must be explained how it happens that the light is conceived into the stone and is given back after some time, as in childbirth. Today we know that Bologna stone was in fact burium sulfide. I love how so many elements of this story are like what if I baked some rocks? What if I had distilled pee? Over and over? So Kunkle was intrigued not only by Bologna stone, but also by all kinds of other luminescent substances. And so when he heard that somebody in Hamburg had created something that glowed indefinitely, he got really excited, and he wrote a letter to Kraft about going to Hamburg to see what this was all about. In some versions of this story, Kunkle and Kraft went together and Bram taught them both how to make phosphorus. After Kraft paid him to do it, But in other versions of the story, Kraft swooped in ahead of Kunkle and paid Brand not only to show him how to make phosphorus, but also to keep that information from Kraft. Yeah, then that version of Storycraft had to work it out for himself, and regardless of which of these is more accurate, both Kunkle and Craft did wind up knowing how to make phosphorus. Kraft started traveling around Europe with phosphorus and other glowing substances, and he did experiments with them before nobles and dignitaries. This included Friedrich Wilhelm, Duke Elector of Brandenburg, Prussia, on April twenty fourth of sixteen seventy six, and then a year later Kraft did the same at the court of Johann Friedrich, Duke of Brunswick, Luneburg and Hanover. Kraft's friend Gottfried Vilhelm Leibnitz, was, among other things, the Duke's librarian, and Leibniz suggested that maybe phosphorus could be used to light a whole room, but Kraft said production of that much of it would be just way too difficult. Even so, the Duke became intrigued with the idea of setting up a mass production facility out in the Hartz Mountains, presumably so the smell of it wouldn't bother people. Leibnitz negotiated with Brand to come to Hanover to work on the project, and he recruited a workforce and started stockpiling lots of firewood and barrels full of urine. It's not a hundred percent clear where all of this urine came from in these stories, Like there's one account that says that Brand had a relationship with a tavern keeper or a brewer or some other person who would have a clientele that peeded a lot, but it's a little vague. Meanwhile, Gustav Adolf, the Duke of Mecklenburg Gustrau, also heard about phosphorus and decided that he also wanted to start a phosphorus factory as well, and this duce representative, Johad Wachi Becher, started trying to recruit Brand away from Hanover. It seems as though Brand tried to use Betcher's offer to negotiate for more money from Hanover, but he wasn't really savvy enough to do this, and instead he just came off as kind of cranky and obstinate, and in the middle of all of this, Kraft started writing to Hanover as well, suggesting that he might actually be a better manager than Brand for this whole phosphorus production project. Leibniz persuaded the Duke to keep working with Brand, and it appears that during all of this Brand did finally document his methods for making phosphorus. He apparently ran a mass production facility out in the mountains for a few months. Then in the late sixteen seventies, phosphorus and the knowledge of how to make it reached England. Robert Boyle, who was one of the founders of modern chemistry, heard about Brand's production of phosphorus from urine and he independently worked out his own way to do the same thing. About ten years later, Boyle then worked to establish a phosphorus production facility in London. As fo this first became more available, demand for its skyrocketed. It went from being a curiosity that people thought may or may not be the philosopher's stone to something that had, at least in theory practical uses. Johann Kunkel figured out how to cast phosphorus into molds underwater and wrote a treatise on the use of phosphorus in medicine called Treatise of the Phosphorus Mirabilis and its Wonderful Shining Pills. Soon, phosphorus was being marketed as a cure, all prepared in a variety of pills and oils and liniments. It was recommended for alcoholism, apoplexy, asthma, cataracts, choleracolic depression, epilepsy, fever, glaucoma, gout, impotence, migraines, paralysis, scrophula, tetanus, toothaches, and tuberculosis. And that is only to name a few. Although phosphates have some medical uses, pure phosphorus does not treat any of these things, and is in fact highly toxic and can be used as a poison. Hennigbrand died around seventeen ten, and about thirty years later Andrea Sigismund Margraf discovered phosphorus in edible seeds. He concluded that people were consuming phosphorus in their food and then excreting it in their urine, and this was the first step in the scientific communities understanding of phosphorus as a chemical element and of its movement through the world in the phosphorus cycle. This is a cycle that begins with phosphate rich rock and moves through water and soil into plants and animals, then back into the water and soil, and then into sedimentary rock. By the early nineteenth century, phosphorus was seeing large scale industrial production thanks to the discovery that it could be extracted from bone ash. Most notably, white phosphorus was used to make matches, which is something that we talked about in a prior episode on the London Match Girls Strike. White phosphorus was really dangerous though it caused a serious medical condition known as phossy jaw, and in eighteen forty nine, red phosphorus was introduced as a less dangerous substitute. By eighteen fifty one, phosphorus was seeing more practical uses, including in manufactured fertilizers. This actually led to a supply and demand problem, which led people to look for new sources of phosphorus. One of these was guano. Guano itself is rich in phosphates, nitrogen, and potassium, making it an excellent fertilizer. The sedimentary rocks that form in places with lots of guano are also rich in phosphates and This led to a land gram for islands and caves with lots of guano. In eighteen fifty six, US Congress passed the Guano Islands Act, which allowed the United States to claim uninhabited islands to mine the guano on them. They were uninhabited by people, they were inhabited by lots and lots of birds. Today, the vast majority of phosphorus is mined from rocks that are rich in calcium phosphate, and about ninety percent of that mind phosphorus is put to one use and that is back to fertilizer. Phosphorus is still used for other applications as well, including plastics, fuel additives, fireworks, rat poison, air, and of course it is still used to make matches. It used to be in a lot of detergents because, like we said earlier, it helps detergents clean better. But too much phosphate in bodies of water leads to algae overgrowth and so a lot of nations to be either banned or strictly limited the use of phosphates indetergent Phosphorus is also used in weapons, including organophosphates which are chemical weapons known as nerve gas, as well as incendiary devices and smoke screens. Ironically, Hamburg, where phosphorus was discovered, was hit with thousands of phosphorus containing incendiary bombs during Operation Gomorrah in World War Two. Yeah, the use of phosphorus in weapons is pretty controversial today, but it still is used. Phosphate rock is not a renewable resource. Even though the phosphate cycle does eventually put phosphates back into rocks, it takes a really long time, and over the past few years there has been some discussion about whether the world is running out of phosphorus. Phosphorus itself is not in very short supply. It's one of the most common elements on the planet, but there's not that much of it that can be mined without huge environmental damage. Like there's a lot of phosphorus everywhere, but only a very few places with phosphorus in a high enough concentration to be able to efficiently mine it. It's not totally clear exactly how much available phosphate there is in rocks that can reasonably be mined, or when we might reach peak phosphorus. Predictions run anywhere from decades to centuries. Because the vast majority of phosphorus is used as fertilizer for plants that directly or indirectly become food. This shortage has the potential to be a global catastrophe, and one of the proposed alternatives is urine recycling or all the way back to just boiling some urine until and explode. I'm glad I got this whole Hennig brand thing out of my system after like three years of saying I should do a podcast on that guy and his weird urine boiling. Thanks so much for joining us on this Saturday. If you'd like to send us a note, our email addresses History Podcast at iHeartRadio dot com, and you can subscribe to the show on the iHeartRadio app, Apple Podcasts, or wherever you listen to your favorite shows.