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12AX7
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Primordial chemicals
I was thinking, what are the most basic, primordial reagents? Like, calcium hypochlorite is a nice oxidizer, but it has to be produced from
something, either by chlorinating lime or electrolyzing a lime-containing solution. Going across the periodic table and thinking up various minerals
of the elements, I remembered that manganese dioxide (the mineral pyrolusite( releases chlorine, a wonderful oxidizer, when added to hydrochloric
acid. This chlorine can then be added to other solutions, lye or lime for example, to give common bleach or the calcium hypochlorite mentioned.
The same thought process can be applied to other chemicals: acids, bases, reducing agents and so on.
Without electrolysis, you can't free HCl from something like NaCl unless you add a stronger acid. The strongest, commonest acid is sulfuric
acid, which can be produced by processing other natural minerals (copperas (ferrous sulfate), burning sulfur).
What else can you think of? How many things are made from it?
Try to think in nearly alchemical terms; no electrochemistry, well unless you want to smelt your own zinc and copper, which have different primary
minerals besides. 
I was having some fun with this thought process, I thought I'd start a discussion on it and see where it goes. 
Tim
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neutrino
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One I accidentally discovered: mixing calcium chloride and magnesium sulfate solutions, then heating the resulting paste to decomposition releases
HCl. It goes something like this:
Ca<sup>2+</sup><sub></sub> + SO<sub>4</sub><sup>2-</sup> --> CaSO<sub>4</sub>
Drying, we get solid MgCl<sub>2</sub> . 6H<sub>2</sub>O. Finally,
2MgCl<sub>2</sub> . 6H<sub>2</sub>O --heat --> Mg<sub>2</sub>OCl<sub>2</sub> +
H<sub>2</sub>O + HCl
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Fleaker
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Cinnabar is one, a reagent practically dug from the earth itself. That's rather primordial...just heat and collect the metallic mercury.
(it's the sulfide, so heating in oxygen atmosphere yields sulfur dioxide).
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nitroglycol
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| Quote: |
Without electrolysis, you can't free HCl from something like NaCl unless you add a stronger acid. |
Not quite true actually. Sodium bisulphate is considerably less acidic than HCl (the pKa of the bisulphate ion is 1.99, whereas that of HCl is around
-7) but you can make HCl from NaCl and NaHSO4, because HCl comes off as a gas, shifting the equilibrium to the
right.
Back on topic, though, it's a good question. KNO3 and NaNO3 are both
naturally occuring minerals, so I suspect you could do some good stuff there. Solvents? Ethanol and methanol come to mind; not most hydrocarbons,
since they are dependent on the petroleum industry.
[Edited on 15-11-2005 by nitroglycol]
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The_Davster
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Methanol and a few other(insugnificant) chems are produced from the destructive distilation of wood. Assuming copper can be processed from copper ore
you can get formaldehyde.
There is also gold.
There is this volcanic lake somewhere that is concentrated sulfuric acid.
K2CO3 with a bit of sodium contamination can be leached from wood ashes.
Nitrates have already been mentioned, and assuming lead can be had from ore nitrites can be made.
I know there is a source for lime in nature, and with K2CO3 from ash, KOH can be had.
Ethanol as mentioned can be gotten from fermentation.
I can likely think of a few more, but for now, just be glad amateur chemistry has not been persecuted to such an extent to make us have to go back to
the ways of the alchemists in obtaining our chems.
[Edited on 15-11-2005 by rogue chemist]
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chloric1
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I like this thread
Well barium was not familiar to alchemist but definately primordial. First dig up natural barite. heat to about 1100 with a coal fire with bellows
with fine charcoal. Add dilute hydrochloric acid to collect H2S directly or dissolve in water to get the hydrosulfide of barium. Boil with sodium
carbonate solution to precipitate barium carbonate and decant the sodium sulfide. Take your barium carbonate and neutralize with nitric acid and use
the nitrate to make barium oxide or peroxide. Or the nitrate can come from barium carbonate and hydrochloric acid and reacting the chloride with
sodium nitrate in excess. Recrystallize the barium nitrate.
Fellow molecular manipulator
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IrC
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I think Cinnabar would be rare and hard to find, but nice if you could. Around here are entire mountains of chalk, easy to roast to the oxide, maybe
even carbonic acid could be made from it. This whole idea could be a great chapter in Bromic's book project, how to make things from what is
around us. You never know, it may be really handy some day, this is the main reason I love the very old chemistry and formula books.
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12AX7
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| Quote: | Originally posted by neutrino
One I accidentally discovered: mixing calcium chloride and magnesium sulfate solutions, then heating the resulting paste to decomposition releases
HCl. It goes something like this:
Ca<sup>2+</sup><sub></sub> + SO<sub>4</sub><sup>2-</sup> --> CaSO<sub>4</sub>
Drying, we get solid MgCl<sub>2</sub> . 6H<sub>2</sub>O. Finally,
2MgCl<sub>2</sub> . 6H<sub>2</sub>O --heat --> Mg<sub>2</sub>OCl<sub>2</sub> +
H<sub>2</sub>O + HCl |
Good point: some chlorides decompose a significant amount. Alkaline earth and transistion metal chlorides (and especially aluminum chloride hydrate)
decompose, giving off HCl fumes with some amount of H2O, allowing muriatic acid to be distilled directly in low yield.
Sulfuric acid of course is had in higher yield from anhydrous iron, copper, or to a lesser extent zinc, sulfates.
Cinnabar is the primary mercury ore, you just have to find it -- mercury isn't very common in the Earth's crust after all, but just like
silver, it's there. Mercury (elemental) and I think the oxide are also present to some extent.
Chalk, limestone and dolomite: all the calcium oxide and carbon dioxide you could hope for, most formations are several feet thick (up to a few
hundred) and span thousands of miles. After calcining to yellow heat for an hour or three (big pieces may need days, cleaving into 1" slabs
would help here) you're left with CaO and a lot of CO2 out the stack, which can be pumped and compressed, or bubbled into a solution for
collection: read up on the Solvay process, which produces CaCl2 as a byproduct for well, given the materials CaCO3 + NaCl, I think you can guess why.
Oh, and let's not forget CaO is also the primordial alkali. Why? 
The magnesium ought to be leachable, perhaps by dissolving a block of dolomite and precipitating CaCO3 with MgCO3 (from more dolomite? Dunno) to give
seperate Ca and Mg (salt) products.
But this is kind of off the direction... a great conversation as well but I was thinking more what you do with it. (Or maybe I'm wasting my time
explaining; this is an interesting enough angle, at least.) Like, my oxidizer example: besides oxygen in air, about the only natural thing you have
is MnO2, which can oxidize Cl- to Cl2. The MnCl2 can be precipitated and reoxidized with oxygen and fire or weathering and time (as happens
naturally). That Cl2 gas can go on to do just about anything, up to and including things like permanganate (which can also be made from pyrolusite
and a caustic fusion, in air), perchlorate, ferrate and so on.
And heck, primordial electrochemistry is worth thinking about, too. It's a lot of effort to mine, roast, smelt, distill and cast zinc anodes,
but it can be done. Copper can be mined, roasted and smelted with a bit more ease, though it needs more fire to cast it (not a problem for a
firetender such as myself ). Electrolyte, well that can be made from whatever,
be it acid, base or a salt. Given enough surface area and a few cells, you can do all the standard electrochemistry, well assuming you can isolate
platinum, and make chlorates, persulfates and the ever most venomous fluorine,
as well as the strongest reducers, the alkali metals (which can in fact be isolated by carbothermic processes!).
Organic chemistry of course all starts with organic chemicals, since it's a waste to start with CO2 and there's so much plant and animal
life available to the desperate Mad Scientist. Finding the source of reagents (oh my, and glassware! ) for these synthesis might prove an interesting angle however.
Tim
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chromium
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If someone can give way to oxalic acid without nitric acid or NaOH then one can use it instead of sulfuric acid to decompose chlorides or nitrates to
volatile acids.
If one has sulfuric acid then magnesium sulfate can easily be got from dolomite.
IIRC ferrocyanides and cyanides can be made from iron oxide and charcoal.
Acetic acid can easily be made by fermentation. When reacted with lime or calcium carbonate it gives calcium acetate that can be converted to acetone.
Lime can be chlorinated to calcium hypochlorite and this with acetone can be used to make chloroform.
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nitroglycol
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| Quote: | Originally posted by chromium
If someone can give way to oxalic acid without nitric acid or NaOH then one can use it instead of sulfuric acid to decompose chlorides or nitrates to
volatile acids.
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IIRC, oxalic acid is found in rhubarb and wood sorrel leaves. I don't know about the concentration, though, or how pure you could get it under
"primordial" conditions.
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12AX7
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| Quote: | Originally posted by chromium
If one has sulfuric acid then magnesium sulfate can easily be got from dolomite.
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Or bitter wells where this occurs naturally -- hence the origin of epsomite (epsom salts).
| Quote: |
IIRC ferrocyanides and cyanides can be made from iron oxide and charcoal. |
IIRC, urea, charcoal and iron. (Saw a synth on here somewhere.) Urea of course is boiled-down urine.
Tim
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Microtek
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Take a look at cavemanchemistry.com. It has many interesting experiments which could be of use to the stranded-on-a-deserted-island chemist.
edit: It seems that site has become commercialized; the experiments used to be freely availible - now you have to buy the book.
[Edited on 15-11-2005 by Microtek]
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S.C. Wack
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Ferrocyanide was made from leather, hair, blood, etc. as nitrogen source back in the day.
This is very stinky.
Obviously this can be dehydrated and heated in a closed crucible with or without potash to obtain KCN, which can be purified with distilled grain
alcohol.
Iodide from burned seaweed.
Tin from SnO2 and coal if tinstone is around.
Sulfur from the local active volcano.
These things, like cinnabar, Chile saltpeter, coal, native copper, etc., are sadly rather nonexistent round here.
From burnt lime or potash heated with aged urine, ammonia. Ammonium carbonate from dry distillation of dried urine. From potash, urine, dirt, and
time, KNO3. HNO3 and NH4NO3 from there. From ammonia dried with CaO, dry NH4NO3, and blown glass, a container of anhydrous ammonia in liquid form.
Numerous products that can be isolated fairly easily from large amounts of certain plant material.
Caveman chemistry dude may have beat me to it, not because he started work sooner, but because he settled for less. Don't look behind you.
Destructive distillation of large amounts of organic things is an art unto itself. See "coke manufacture..." in vol. 2, "bone oil"
in vol. 1, and "wood, destructive distillation of" in vol. 7 of Thorpe's "A Dictionary of Applied Chemistry".
[Edited on 16-11-2005 by S.C. Wack]
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mick
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In William Prescott's (1796-1859) History of the Conquest of Peru, the Spanish were running out of black powder with no chance of being
re-supplied. They made their own by sending an expedition down an active volcano to get the sulfur. I assume a suitable grade of carbon and potassium
nitrate would be straight forward for the local expert to manufacture on site in those days.
I doubt it the people who descended the volcano would be very healthy after. I wonder what would have happened if they had not got their muskets
working.
mick
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chloric1
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Well, Mick, Lima would not be a modern megalopolis and there would not be mesitos. And the natives definately would not be speaking spanish. Would
the world be better place? We never will know. It would be cool if all of Peru looked like Machu Piccu(sp?)
Sorry off topic. I think saltpeter occurs naturally in caves!
Fellow molecular manipulator
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The_Davster
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Methyl salicilate can be gotten from the wintergreen plant, which with base can be converted to salicylic acid.
SC Wack, do you have any books on destructive distillation of organic materials? I find the idea rather interesting. EDIT: not destructive
distillation of reagents, but of natural plants and the like.
And electrolysis of various things should be able to be done as long as one can get metals to assemble the battery. Which in itself opens up a whole
other range of compounds which can be made!
[Edited on 16-11-2005 by rogue chemist]
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IrC
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"I think saltpeter occurs naturally in caves!"
Formed underneath piles of bat guanno (crap) by the reaction of the bat droppings with the minerals which make up the walls and floor of the cave,
from millions of bats over many years. Caves were one of the major resources in the days of the wooden sailing ships for replenishing black powder
stores.
[Edited on 16-11-2005 by IrC]
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froot
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Iron pyrite (FeS2) occurs in abundance in some regions.
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
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Magpie
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I agree that this making chemicals from nature's raw materials is at the heart of this forum.
I know where there is an inactive stibnite mine not too far from me. Some day I'll revisit it then make my own antimony.
The single most important condition for a successful synthesis is good mixing - Nicodem
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12AX7
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Cool. If you find some nice sized and shaped crystals, I'd love to have some in my collection. Plus maybe some ore for similar purposes
Tim
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Magpie
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12AX7 I'll bring back plenty of ore and you will be welcome to have some. Also the Sb. But don't be in a hurry as I won't be making a
special trip to get it. The mine happens to be near some fine trout fishing and that would be my main reason for getting over that way.
The single most important condition for a successful synthesis is good mixing - Nicodem
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Theoretic
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"Sulfur from the local active volcano."
A true gem. I can imagine Mr. Wack returning with his pockets full of sulfur,
his clothes stained yellow, with multiple holes from lava droplets, a huge grin and 15 m/s (down the slope!), shouting "Sulfur! We have Sulfur! I
am a true Mad Scientist!"... then the volcano erupts and further black smouldering holes appear in the rags-that-pass-for-a-labcoat... and he
doesn't even notice.
Then for the next week he's bedridden with SO2 poisoning and prohibited from experimenting for that period.
"Iron pyrite (FeS2) occurs in abundance in some regions."
...which can be just left to sit there, and the oxygen and moisture will turn it to sulfuric acid and ferric sulfate:
4FeS2 + 15O2 + 2H2O => 2Fe2(SO4)3 + 2H2SO4
The ferric can be reacted with CuS ore to give copper sulfate:
CuS + 4 Fe2(SO4)3 + 4 H2O => CuSO4 + 8 FeSO4 + 4 H2SO4
Edit: the ferric can also be heated to total anhydrity and distilled to give SO3, this can be reacted with HNO3 obtained using your sulfuric to give
nitrosulfuric acid <=> nitryl hydrogensulfate (NHS, yes I spot the pun) and this is a very good nitrating agent, giving higher yields than
sulfuric/nitric. And plant oil/animal lard reacted with alkali (soda, potash, KOH, NaOH) gives fatty acids and glycerine. I can foresee NG! Nitrate
cellulose with NHS and get NC, this together with NG gives blasting gel.
If one wants gunpowder AN/C is a good one, hygroscopic though. It's roughly as powerful as NG-based propellants, and I assume ANFO would be a
better and non-hygroscopic propellant (again, plant oil can be used as fuel).
Or the sulfide could just be left there (as with pyrite, preferably moistened) to oxidize naturaly to CuSO4.
[Edited on 18-11-2005 by Theoretic]
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stygian
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Any ideas on primordial calcium carbide?
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The_Davster
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CaO + C and arc melting with a huge ammount of amps in a graphite crucible. I wonder if an arc welder could do this.....
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woelen
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| Quote: | Originally posted by rogue chemist
arc melting with a huge ammount of amps |
Primordial ?? I think I learned something new again about prehistoric times
?
But, the idea is nice, although I think it will be quite hard to do this at home.
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