A follow-up post to "Distillation Daydreams" where I give some details of my recurring fantasy of recreating human technology on my own, possibly in the distant past or alone on a foreign planet.
Some technologies enable other technologies. Let's talk about the sequence of technologies that give you access to different elements of of the periodic table.
If you're on a planet with life, you're in luck. You can thermally decompose organic matter, like dried plants, in a low oxygen environment to get charcoal. Now you have access to a fairly pure source of carbon; one element down. Charcoal burns well, and you can use it to get high temperatures for roasting and distilling things. Also, if you mix powdered charcoal and mineral oil and then ram it into a tube, you get a carbon paste electrode, which is useful for isolating elements by electrolysis. I think graphite powder works better than charcoal powder, but it's way easier to get charcoal powder, so that's what we're doing. I don't know what you can use besides mineral oil as a more readily available liquid binder. It would be awesomely convenient if you could use triglycerides (found in fats/oils), or wax esters (found in beeswax, carnauba wax, sperm whale "oil"), or resin acids from trees. That's something I need to investigate.
Nitrogen gas is in the air. You have access to it already, on Earth anyway. But it's not super usable in that form. Add in oxygen or hydrogen to get more useful chemicals. For example, you can distill protein to make ammonia gas, NH3, and dissolve it in water to get ammonium hydroxide NH4OH.
If you burn organic things, you get ash and charcoal. If you burn things hotter, you get just ash. Ash is mostly calcium carbonate, CaCO3, also called lime. If you heat the ash up even hotter,- if you roast it - then you can drive off CO2 to get calcium oxide, CaO, also called quick lime. That's not direct access to an element, but it's close, and CaO is a very useful chemical for lots of things including other element extractions. For example, if you have a brine with magnesium ions, like evaporated ocean water, you can add CaO to precipitate magnesium hydroxide, Mg(OH)2. Again, not a pure element but it's progress.
Lime is the main part of ashes, but there can be are other things like calcium chloride and salts of sodium and potassium, and these have much higher solubility in water than lime. The ash of deciduous trees tends to have more potassium salts, especially K2CO3 and some KCl, and the ash of plants that grow in salt water tends to have more sodium salts, especially NaCO3 and some NaCl. You can wash these ashes to dissolve the potassium or sodium salts, evaporate off the water, and then roast to get potassium oxide, K2O, and sodium oxide, Na2O, respectively. You need really high temperatures, but it's possible. Make a kiln, burn a lot of charcoal; you can do it, kid. I believe in you. The oxides will spontaneously react with moisture in the air to form hydroxides, KOH and NaOH, which have a million uses. You can also get elemental iodine from seaweed ash, but there are a lot of steps. We'll talk about that one later.
In the last post on distillation, we talked a lot about getting sulfuric acid from minerals, and how it also enables you to get hydrochloric acid, nitric acid, and phosphoric acid from chloride minerals, nitrate minerals, and phosphate minerals. Chloride minerals are free in oceans and seas. How do you get nitrate minerals? Wellllll.... If you keep peeing on a bed of straw for months, bacteria will turn the ammonia in your urine into nitrate, which will bind to trace alkali/alkaline metal in the straw, or to the ammonia, forming ammonium nitrate. Congratulations, now you have a a form of nitrogen with oxygen instead of hydrogen. Nitrate salts are good oxidizers. They're a useful component of gunpowder, among other things. Calcium nitrate can also form as an efflorescence where manure rests on calcium carbonate. So maybe poop on some ashes or limestone, if you want nitrate salts and you don't want to pee on straw? I don't know if bacteria are a necessary part of the efflorescence process. Maybe you can do it even on a planet that doesn't have the right bacteria.
So now we know how to get nitrate minerals. What about phosphate minerals? Bones and teeth have a little bit of calcium phosphate, but not nearly as much as you might think given how hard they are. Still, you can roast them to drive off the organic molecules as gas and and eventually get phosphate ash. Or you can get lucky and find some apatite in the ground, if you know your rocks.
Rocks also have heavy metal ores. If you crush rocks, you can use density methods to separate out the light silica from heavier metals-bearing ores. There are tons of density separations methods and machines, like gold pans and sluices and shaker tables. You don't even need water generally, although it helps. You can totally gold-pan in the desert. One of my favorite density separation methods is gravity-assisted centrifugal separation, in which you pour sand down a helical slide with a curved bottom, like the plastic slides you might find on lots of children's playgrounds. The lighter sands ride up the curve toward the outside and the heavier sands don't. You might not have access to a helical tube slide if you're in the distant past or on Mars; I'm not saying it's the best option. But there are lots of options. Density separation will give you sand with a high iron content, with lots of iron oxides and hydroxides. You can get iron metal from this, but it's not as easy as you might think. We'll talk about it later.
I've heard that once upon a time, in Roman times and before, you could walk around places with exposed bedrock and find veins of lead, and now you mostly don't because we mined it away. All the lead being mined away might not be a problem if you're in the distant past or on a new planet. If you can find veins of it, then lead is pretty easy to mine. You can even melt lead with a wood fire. Setting a fire against a rock wall and dousing the heated rock wall with water is also a good way to creature stress fractures, if you want to mine other metallic ores and you don't have a pick.
Besides the immediate benefits to mood of having ores and metals, and besides their use in structural members, it's also really nice to have at least two different metals if you want to make a battery, though you can also do it with just lead and lead oxide. At first in this fantasy, the metals aren't going to be alkali/alkaline metals, like Na, Mg, K, Ca, because they're very reactive and hard to separate from oxygen unless you already have batteries for electrochemistry. Also we won't start with aluminum metal, which is also too reactive to isolate from oxygen by roasting. What other metals exist in planetary crusts in appreciable quantities? Besides iron and lead, the most abundant metals that you can get at by roasting are mercury, tin, zinc, and copper. Bismuth, silver, and gold are less common, but were also discovered in ancient times - bismuth a little later than the other two. Arsenic and antimony are metalloids that are also accessible: fairly abundant, low melting points, not too crazy reactive. I don't think that anyone makes batteries from those metalloids directly, but they're useful in alloys. Lead with antimony is particularly good for batteries and bearings and bullets. Arsenic with copper, in-place-of or more often in-addition-to tin, makes a good hard bronze that also casts well.
Once you've got metal ores separated from rocks or river bed sand, it's a normal part of mining operations to heat the metal to drive off oxygen or sulfur. If you've got multiple metals, you can probably separate them a bit by melting point. If you've got an alloy that doesn't want to separate by heat, some metals will dissolve more readily in specific acids than others, e.g. silver can be separated from gold with nitric acid since the former is soluble in nitric acid and the latter is not.
So hopefully one way or another you can isolate some metals of decent crustal abundance. Once you have metals, you can use them to make batteries. The original battery design, the Voltaic pile, had stacks of metal plates (two different metals alternating) in a tube, separated by sheets of cellulose, and covered in salt water NaCl brine as an electrolyte. That's all it takes. And you don't even need the cellulose or the tube. Some pairs of metals work better than others (those with dissimilar Standard Electrode Potentials). Acids also make good electrolytes. And I think bases also make decent electrolytes. Basically, there are lots of options. Batteries are not super duper difficult to make.
One of my heroes, the chemist Humphry Davy, just a few years after the Voltaic pile was invented, made huge batteries to split mineral salts by electrolysis and discovered a ton of new elements. You've lived with batteries all your life and have probably never isolated any those elements. The only thing that separates you from the great Humphry Davy is that you're not making giant batteries and electrocuting rocks. You could probably do it this month, if not today or tomorrow. I could too and I haven't - I'm not trying to be too judge-y. But there's not that much that separates us from great scientists besides our lack of will to do things bigger.
What if the only metal you have is lead? Then maybe you can make a lead acid battery and use carbon paste electrodes for wires. To make a lead acid battery, you will also need lead oxide and sulfuric acid. Lead oxide can be made by heating lead in air, and we've already talked about sulfuric acid in the last post. Here's where I should go into more detail about lead acid battery design: ...
One way or another, let's assume you have batteries now and also conductive wire. Congratulations, you can now do electrochemistry. The first thing you'll want to to do is split water. Now you have hydrogen gas and oxygen gas. Their mixture, oxyhydrogen, is kind of terrifying. It likes to explode and turn back into water. It burns so hot it can melt platinum. It's awesome. If you have access to animals, you might be able to store the two gasses separately in bladders. That's how they used to do it. No balloons, just bladders. There are probably other options. Maybe a leather bag waterproofed with tar or something.
The next thing you'll want to electrolyze is NaCl brine. Do this, and you get sodium hydroxide. NaOH, and chlorine gas, Cl2, alongside some oxygen and hydrogen like before. Chlorine is almost as scary as oxyhydrogen. Chlorine both destroys metal labware and kills people with great facility. If you want an easy source of sodium hydroxide without the chlorine, you can instead electrolyze sodium carbonate brine. But it's a lot easier to get sodium chloride than sodium carbonate, so let's talk about what you can do with the chlorine gas.
Spoilers: you make it into hydrochloric acid. We've already talked about making hydrochloric acid by distilling sulfuric acid with sodium chloride. We're making it again now in a different way because sodium hydroxide produced by electrolysis is really useful, but it produces chlorine gas as a byproduct, and chlorine is horrible. If you're making chlorine gas at scale, you need to do something with it at scale, and hydrochloric acid is a great option. I think PVC is also good for chlorine capture, but we're not ready for that. So, how do we combine hydrogen with chlorine? Bubble both gasses into water. Do it for a long time, like overnight, to saturate the water with those gases and displace dissolved oxygen, since oxygen can foul the reaction. Now shine UV light on it. That's it. They'll combine. It's awesome. I'm not sure what the exact wavelength cutoff is for splitting the Cl2 bond. I've seen a demo where blue light did nothing and another where blue light worked. So ... 400 nm or less, maybe? Ultraviolet light definitely works though. If you have a test tube with a stopper, you can shine a black light on it and the stopper pops out along with a cloud of hydrogen chloride. It's a wonderfully quick reaction once you activate it with EM radiation of right wavelength. It's basically a little canon that makes poison vapor, and it's a good idea to do the reaction in plastic instead of glass to avoid shrapnel. Now, sunlight has UV and I bet you can do the reaction under sunlight. What if you want to make a UV lamp? Is there a primitive way to do that? Not that I know of. Mercury vapor lamps give off UV radiation, but we're not ready to make glassware yet. We'll talk about it later. Probably after we've smelted iron and isolated boron. Anyway, shine a light, get some hydrochloric acid, keep it stopped up until you need it. It's way safer than chlorine gas.
So that's the chlorine taken care of. You know what the NaOH is really good for? You can make salts of fatty acids that are a component of triglyceride fats and oils. The salts are called soap, and the leftover glycerol can be nitrated with nitric acid to make nitroglycerin, which is good for mining, among other things.
Electrolysis can also be used to make small amounts of elemental alkali and alkaline metals, like elemental sodium, potassium, and calcium. They're kind of too reactive to be very useful, I think. Like, sodium metal is good for... heat transfer in nuclear reactors? We're not that far along in the fantasy yet. One alkaline metal that *is* awesome and useful is magnesium. It's a great lightweight structural metal, and it's one of the most abundant metals in the earth's crust and it's also abundant in sea water. Despite its use as a structural metal, it's also really reactive. It has enough reactivity to be awesome and enough passivity to to be useful. I really love magnesium. You know who first isolated it? That's right: Humphry Davy.
A good way to get magnesium metal is to get magnesium hydroxide by reacting CaO or Ca(OH)2 with magnesium-bearing brine, and then react that with hydrochloric acid to get to get MgCl, and then electrolyze the molten chloride salt. You can also just take magnesium oxide, MgO, and reduce the oxygen off with something that loves oxygen, like elemental silicon or carbon, but we haven't talked about isolating silicon yet and doing it with carbon requires really high temps. Magnesium will show up later when we talk about isolating elemental titanium.
On the subject of reactive structural metals, can we get aluminum by electrolysis? Yes, but it's hard. First you need aluminum oxide. That's the easy part; heat clay with hydrochloric acid, which dissolves alumina (producing aluminum chloride) but not silica. React the aluminum chloride with sodium hydroxide to get aluminum hydroxide and roast that to get aluminum oxide. Here's the hard part: You have to melt aluminum oxide before you electrolyze it, and that requires very high temperatures. You can lower the necessary temperature by using a mineral called cryolite as a flux, but cryolite is terribly rare in nature, and the only real way to get it is to make your own. To make your own, you need hydrofluoric acid, which is one of the scarier chemicals to me - considerably worse than oxyhydrogen gas or chlorine. You can make hydrofluoric acid from fluorine bearing minerals like fluorite and fluoroapatite, but... don't. Don't make hydrofluoric acid. Unless you're a immortal time-travelling cyborg, I guess? But even then, do other things first. See how far you can get with magnesium metal. Instead of using cryolite, I hear you can use some potassium or sodium metal to help with the general effort of electrolyzing molten aluminum oxide. That makes aluminum really really expensive - and still pretty dangerous - but it can be done. Also, you can electrolyze a mixture of alumina and copper to make an aluminum bronze, I hear. Cryolite is the reason that aluminum is now cheap enough that lots of people don't even recycle it, when it used to be more valuable than gold, but cryolite is something you do in a late stage of the Elemental Tech Tree, not as soon as you can. Like, hydrofluoric acid attacks basically all metals besides nickel and nickel alloys, so you should get nickel before you try to make it. And it attacks most rubbers, but butyl rubber has good resistance, so learn to make that first. For plastics, learn to make PVC or polypropylene. Now you have a reaction vessel, rubber gloves, and a storage bottle. This is a boss fight and you need to come equipped. Also, you'll need health potions. Calcium gels like calcium gluconate gel are used topically if you get a burn. They don't do enough. You will still die. Calcium and magnesium antacids are also used internally in the case of burns. They also don't do enough. Calcium gluconate is also used intravenously to treat hydrofluoric acid burns, and if you're tech tree isn't grown enough for aseptic injections, you probably shouldn't fuck with hydrofluoric acid, especially not hot concentrated HF, as it comes when you produce it. Also, where are you going to get these fluorine-bearing minerals? Ha, gotcha. Can't do it. Moving on.
This is next bit is... technically part of the elemental tech tree, I think. You can use mineral acids to turn cellulose into glucose, which you can ferment to make dilute ethanol, which you can concentrate by distillation or freeze-jacking. Ethanol will be useful later for phosphorous extraction.
Isolating iodine from seaweed ash: Seaweed ash contains sodium iodide and potassium iodine, NaI and KI, among other things like calcium carbonate, sodium carbonate, sodium chloride, and magnesium chloride. One way to get iodine out is to react the ash with copper sulfate, forming a copper iodide precipitate. Remove the precipitated copper iodide and heat with sulfuric acid to form copper sulfate again and iodine will come off as condensable vapor. Is there a method that doesn't require copper? I don't know. I'll look into it.
Isolation of phosphorous from phosphate salts: ...
Boron: ...
Bromine: ...
Liquid nitrogen: ...
Noble gasses: ...
I think now would be a good time to talk about making iron and steel, which make other things possible, like arc furnaces to get silica and large scale mining machines to get rarer metals.
...
Titanium: The most commercially important titanium ore is ilmenite (trigonal FeTiO3), which is weakly magnetic. You can pick it up with a strong magnet and then pick out contaminants of iron oxides/hydroxides with a weaker magnetic. Another good titanium ore is titanium oxide, TiO2. It has a ton of different mineral polymorphs, including rutile and anatase. TiO2 isn't too hard to find on earth. It commonly makes up a moderate fraction of igneous and metamorphic rocks, like a few percent by mass. It's often mined from sedimentary sands that were weathered from igneous rocks, but if you don't have a beach full of TiO2 or FeTiO3, you can also crush igneous rocks yourself and sort the sand by density. The main way people get titanium from TiO2 industrially is the Kroll process. First, heat TiO2 in chlorine gas producing liquid TiCl4. You can increase your yield by mixing in some elemental carbon with the TiO2, which grabs onto the oxygen. Next, reduce the TiCl4 with liquid magnesium metal, leaving behind elemental titanium sponge. To make it usable, you then break up the sponge, heat and compress it into ingots, and the forge the ingots into jets, jewelry, and hip joints. If you start with FeTiO3 instead of TiO2, you can try to remove the iron before making TiCl4, perhaps with sulfuric acid, or you can try to remove it afterward in the form of a ferric chloride (FeCl3) contaminant.
Gallium: ...
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