It's crazy to think how much my life has changed since first finding this channel. I have got married, had a kid, bought a house, paid it off, and had my 12th anniversary in the meantime. The videos have stayed at the same high quality. No annoying sponsorships, no over the top clickbait, just good repeatable information. Here's to another 15 years or so, Mr. Rage.
Good on ya. You are on here and speak properly. So use your intelligence to organize your community, and teach chem to whoever will listen. We won't be able to afford decent housing soon, but that doesn't mean our future generations can't.
I thank you on behalf of the European amateur chemist (or wherever sulfuric acid is not available) for providing another alternative method to make sulfuric acid!
@@aga5897 No in either of these, but sulfuric acid in high conc. is banned in some places, and it is often hard to come by for amateur chemists even at lower conc. as I often heard people complained about it.
@@aga5897 It is often out of reach for amateurs as I often heard the struggles from other people. The US has it as a drain opener which is indeed a very luxurious thing to have.
At first I was like, what? No, this is completely different, this is about amateur access. But computing pi in dumb ways is kind of like amateur math, doing it just for fun, so yeah, it kind of is the same thing
@NurdRage For really hard to filter stuff, I vacuum filter through a 10cm buchner funnel and filter paper with diatomacious earth. I really helps to add a round piece of course fiberglass cloth under the filter paper (slightly smaller than the filter paper): it adds lots of flow channels and also supports the filter paper so it won't blow through the holes in the funnel. You can also use plastic screen if it's resistant to whatever you're filtering. Just pre-wet the filter paper using water+DME and keep running the DME water until it runs clear. Rinse the flask and you're ready to go. Sorry for the late edit. One more thing that can really help: Seal the top of the funnel with a flexible film, like Saran wrap or even film from a condom (unlubricated 😉). It will compress the stuff above the filter and improve throughput. Caution: 14.7 PSI on a 10cm filter is (if I did the math right) almost 180 pounds of force! Wear safety glasses! And as I also found out, erlenmeyer flasks with a side arm are not always vacuum rated! Fume hood window & safety glasses saved me from my own ignorance/stupidity.
I was also playing around with the idea and found a way of making sulfuric acid from oxalic acid by heating oxalic acid together with regular magnesium sulfate epsom salt. when melted together it turned into a white sludgey liquid, which contained the sulfuric acid, which then could just be distilled off. Its also a really efficient method when making nitric acid, as potassium nitrate could just be mixed in with the dry oxalic acid and magnesium sulfate powder mixture. When heated the potassium nitrate reacted with the sulfuric acid and produced the nitric acid, which also could be distilled with ease.
Yeah, I actually thought about this method being possible a few years ago. It seems like it violates the “can’t make strong acid from weak acid” principle, but it actually doesn’t. It’s because that’s not the only force at play here it isn’t as simple as the oxalic acid protonating a sulfate ion and generating sulfuric acid. That kind of reaction is still unfavored. But you’re dealing with the power of Le Chatelier‘s principle. Oxalate is an unusual anion, due to how insoluble some of its salts are. And those salts are still mostly insoluble even in acidic conditions, which is rare. So the reaction is pushed forward by the mass action and formation of insoluble iron oxalate, NOT the protonation of sulfate. That still happens, but it needs the much stronger driving force of removing oxalate from the equation to overcome the unfavorable energy barrier.
@@WielkiKaleson that’s what I said. The sulfuric acid is formed as a result of the oxalate being insoluble. That force dominates even though what you would explicit to happen is nothing. Just a mixture of oxalate, sulfate, and hydrogen ions in solution. Also for a “weak” acid oxalic acid is actually fairly acidic with a pKa of 1.25
@@spiderdude2099 In fact, in case of a solution, writing "H2SO4" can be missleading as it suggests such a species if floating around. On the other hand, although H2C2O4 is mainly not ionised, the ionised form is the player important here... So, I am not religious here.
The method using copper sulfate has worked out pretty well for me so far so I'm also puzzled by it not working out here. Admittedly it is a real pain to filter off the copper oxalate and it always will be. For me it usually does come out by letting it settle or running it through the frit several times. The only ways my procedure differs from yours is the fact that I'm using smaller amounts of reactants in less concentrated solutions and not heating anything. In fact the oxalic acid gets pretty cool upon dissolving so it's usually below room temp. The lower concentration of reactants also makes the suspension of copper oxalate thinner which might help it settle. Another thing I want to mention is that a similar process can be done using sodium bisulfate and hydrochloric acid. By adding finely powdered NaHSO4 to concentrated HCl it will react to form sodium chloride which is sparsely soluble in concentrated HCl. It doesn't look like a lot is happening but upon reacting these in hot solution, cooling, filtering and distilling one actually obtains quite a bit of sulfuric acid. The yield sure isn't too high but the nice thing is that you get your unreacted starting materials back. Unreacted HCl just distills off and NaHSO4 precipitates out while concentrating the sulfuric acid. For lack of a better alternative this is usually my go to route. Furthermore there's this which i haven't yet tried myself: www.sciencemadness.org/talk/viewthread.php?tid=79548 (there should be a url there, i hope yt plays along) Also just let my say that you made one hell of an amazing video again which is of great value to the amateur chemistry community. You never seem to disappoint. Thanks!
I can't believe you could post an outside link. RUclips have deleted so many of my comments with links I don't even consider it possible anymore. I wonder what it is that make some links allowed and most not.
I am unsure about the practical usefulness of this process, but it is very elegant and smart, nice job. Your videos have taught me a lot and this one doesn't disappoint either.
I wonder if chilling the copper sulfate solution prior to oxalate addition would slow crystal growth and thus create "bulkier" particulates that would be able to be filtered on at least a frit if not even a paper filter.
i hope you'll show the same method for making nitric acid as well, since magnesium nitrate does work for making nitric acid and it's much easier to distill than sulfuric acid it's the best method for making nitric acid requiring no high temperatures or expensive sulfuric acid
I bet you are unaware of the impressive number of people that became chemists fom your inspiration just by simply helping me pave my way to it since I made sure to perpetrate the passion for it and I'm pretty confident I'm not the only one.
All through this video, I was thinking about the big bag of copper sulphate out in the shed... so thanks for answering my inevitable question without me even having to ask it. :)
Ferrous sulfate solution should be a nice seafoam green color. I noticed your ferrous oxidize when your water was introduced. If you can force the orp to a double digit number you can keep your Fe2 from turning into Fe3( your pH should be rather low especially after OxAcd so you avoid the risk of dropping out fe3 at pH3.6) the reason i mention this is that Fe3 is soluble in the presence of oxalate. So your fe3 is inadvertently taking up oxalate . Not sure how that will affect your yeild but it keeps your oxalate oxalic acid in equilibrium perhaps decreasing your yeild. Just a thought.
Potentially the pore size of the is larger than that used by other amatuers. It's always interesting to hear more examples of things that go against what you're taught in highschool/undergraduate chemistry classes!
That's what I was thinking. You might not even need a high-powered (expensive) one. Copper II Oxalate has a density of 6.57 g/cm3. Presumably you could DIY a centrifuge to separate something more than 6 times denser than water, even if it is in molecule-fine particles. Just be careful to balance!
6:00 As a reducing agent you can use regular iron wool. It reduces Fe3+ to Fe2+ while going in solution as Fe2+, gives a purer product and can be easily filtered off.
A slightly easier, and possibly more time saving way to photodecompose the iron oxalate would be to use a UV lamp. Those can be fairly cheap, only run on similarly cheap electrical power, and are sometimes even more powerful than the UV you get from exposure to the sun, especially if you place the beaker directly under it and blast it for a while up close and in a contained area.
Excellent! after googling I found that iron sulphate heptahydrate is = ferrous sulphate, te one easy to get that I use on the garden. Oxalic acid is also easy to get as wood bleacher.
I do enjoy the clarification of parallel methods that may (or may not) work. It's fascinating how transition metals with supposedly equivalent behaviors end up being entirely different when you go to try the method. Should the metal oxylate form? Sure thing. Does it? Probably. Can you separate it? Not at all, yes, and maybe.
This was a chemical reaction I'm curious about, never knew they was a easier way to recover sulfuric acid using oxalic acid. When salts like sodium or potassium sulfate are form they really difficult to make sulfuric acid unless using a way more stronger acid then sulfuric acid, or a electrolysis that involves to much current. Oxalic acid do form alot of insoluble metal salts... It's a miracle that we can do this, this why I love this reaction.
Another side note, could have tried less water when using copper sulfate, I could have produce a thicker crystal of copper oxalate, then later on dilute it down if required. It really makes us curious weither the yield was good.
Don't they usually use some polyaluminates to flocculate more effectively? great vid tho. I really thought the magnesium would work; ion radii are similar so you'd think it would just electrostatically sort of work out... clearly more going on of course :)
I feel like if you could continuously filter the precipitate out the magnesium yield would go up. Like use a cheap aquarium pump to cycle it through a filter. Might take longer but bulk processing "hands off" is still pretty good.
About copper oxalate. You could try some classic ways to get bigger particles. For example slow addition and performing this reaction in hot solution to promote slower crystallisation. Those are at least from the top of my head. Or you could also try filtering through a layer of celite if you have some, maybe it will be able to stop the precipitate. Anyway I now want to see the yield of H2SO4 from this. 😅
If oxalic acid is strong enough to displace H2SO4 from FeSO4, could this be modified to work with a nitrate salt (say, CuNO3) that would be rendered insoluble upon reaction with oxalic acid and produce HNO3? Im aware it's probably far more efficient to use the NaHSO4 and KNO3 distillation method, but it does make me curious if its possible on a theoretical level. Another absolutely genius, awesome video!
Oxalic acid solution added to calcium nitrate solution precipitates calcium oxalate and yields dilute nitric acid. Let precipitate settle, decant, filter, distill. This also works with CuNO3
@@jbone877 Very interesting. Thanks for the information. I had a hunch it would work but i was curious if anyone could confirm it. Oxalic acid is incredibly capable for a weak organic acid. It also works great for cleaning MnO2 and FeCl3 stains which are a pain to deal with (from personal experience).
@@stefangadshijew1682 This is true, I suppose I should have clarified that I meant the technical term "weak acid" (an acid that does not fully ionize in solution). I'm still a noob amateur chemist learning the ropes, but it's my understanding that as a general rule, weak acids cannot displace strong mineral acids (H2SO4, HNO3, HCl, HBr, HF, HI is a bit of a weird case though) from their respective salts in any meaningful amount. For example, you can't make HCl from adding glacial acetic acid to table salt, but it absolutely works with heating a mixture of salt and bisulfate and bubbling the gas into water with a funnel trap as NurdRage has demonstrated, and i have personally made HCl that way. I know this rule doesn't always apply in every situation though because I've read you can make the strong, volatile mineral acids from the action of hot phosphoric acid, technically a "weak acid", on their respective salts, you just have to be mindful of the fact hot H3PO4 etches glass at those temps.
@@keithm5378 Hey there! :) The "rule" of "strong acids liberate weak acids out of their salts" isn't really a rule. The rules at play here is the law of mass action and the principle of La Chatelier. You've got an equilibrium between two acids that favors the formation of the weak acid. But then you also have other equilibria or non-equilibrium-reactions that can shift the equilibrium to the product side. If you generate HCl with H2SO4, you are also generating the stronger acid with the weaker acid. (pKa -6 and -2 respectively). But since you are distilling off the HCl, there will always be new H2SO4 and NaCl consumed and the reaction goes to completion. Those precipitation reactions are exactly analogolous.
If using CuSO4, I've had good results freezing the copper oxalate suspension prior to filtration. Upon thawing, the majority of the precipitate settles to the bottom of the reaction vessel in a relatively homogenous cake, making decanting viable prior to filtration.
This reminds me how I once made (rather dirty) HBr without distillation. I only had KBr as a source of bromide, so I first mixed it with calculated amount ZnSO4 and using fractional crystallization separated K2Zn(SO4)2, then used oxalic acid to liberate HBr from the remaining ZnBr2. Rather absurd process, but it worked.
NurdRage is Da Boss ! One way to purify/concentrate Sulphuric is to boil the hell out of it until the fumes become thick. Then add a splash of 3% H2O2 if it's brown. Amazingly that actually works with no dramas, in my case at least.
@@NurdRage Question: do you ever get contact from the SM folks from back in Your days there? I did, saying they missed me. That's like saying they missed a hole in the head, which was a bit odd.
Not really, and its been so long that i'm sure more than half the people i once knew likely moved on. so even if i did come back there wouldn't be anyone to recognize me.
If you mean dry distillation of the sulfate salts this is viable (it has been done for centuries) but involves very high temperatures (>600°C), it can't be done in ordinary borosilicate lab glass, and it is very dangerous.
You are very, very wonderful. I have learned a lot and a lot from you. I want to ask for your help. Can you make a video about the synthesis of sodium ethyl sulfate and then the synthesis of nitreethane from it?
You can also try bubbling hydrogen sulfide into a solution of copper sulfate; as a result, copper sulfide precipitates, leaving sulfuric acid in the solution. Hydrogen sulfide can be produced by heating sulfur with paraffin.
@@NurdRagewell, experienced amateurs with a proper setup can definitely handle hydrogen sulfide. It's toxic, more than chlorine and nearly as much as hydrogen cyanide, but the smell is so disgusting and strong that anyone would notice being exposed and evacuate the area long before the dose becomes unsafe. But if it can be avoided it should definitely be avoided.
@@user255 Yes, I know that, it's odorless at more than 100 ppm due to desensitization, but long before the concentration rises to dangerous levels you notice its presence pretty evidently and this is enough to evacuate, wear a respirator or take any action.
From a molecular bio approach, I think centrifugation is probably the best way to seperate the milk of coppernisia you made, though this requires a centrifuge. If you have one already this might be worth exploring
You mentioned acetic acid off hand, and that made me wonder anout using perocetic acid for making rust, instead of going the ferous chloride route in a previous video, for rust. I know rhe advantage of HCl is that it works faster, but I've had visually satisfying results using 30% acetoc acid with scrap steel, then adding the peroxide to oxidise it later.
I have been watching your videos for so long it's ridiculous; I just have a quick comment on a possibility for an improvement in this one. Would there be any possibility of improvement in the copper method using a very fine Celite? Or rather more specifically, would you be able to separate an extra fine celite powder from the distillate and then be able to use the resulting solution? Unfortunately instead of my original college degree being chemistry (like 7 years ago), I decided to go with Finance, so I truly don't know if there's any major issues with this thought, but if you or anyone else cares to respond, I would be thrilled to gain any knowledge y'all have about this process!! =)
As cheap as off grid solar is nowadays , I don't see any downside to using it for a continuous electrolytic chemical factory , for producing all sorts of useful stuff , like chloratea , perchloratea , acids , whatever . You can have a shed or garage full of Pauling furnaces running 24 / 7 . Sure they are inefficient , but , once you have your PV setup , the rest is just childs play and it can run indefinitely courtesy of the sun , assuming you have enough storage capacity to run that long , and , enough panels to keep the storage bank topped off .
Centrifuging to speed up the sedimentation of the copper oxalate? Freezing the solution with the hope the ice crystals will compact the copper oxalate particles?
Do you think aluminium sulfate could be used instead of ferrous sulfate. It is also insoluble in water, so it should be nearly the same reaction, or is there something more to ir
Does this mean ebonizing wood with iron (II) sulfate also produces small amounts of sulfuric acid in the wood after the iron tannate complex forms? I know you say it doesn't work with other acids but if they weren't reacting there wouldn't be tons of black complex crashing out and dyeing the wood.
How does the yield compare to dry-distilling the Iron Sulphate directly, like back in the days of alchemy? Suppose I bought a 50lb sack of the stuff because it's not particularly expensive, and making an iron retort isn't a problem.
Yes, that works - to a certain extent: because the reaction mixture gets hot (so it needs to be cooled down well), and the hotter it gets the less SO2 dissolves and reacts.
@@ae-bd5grsimply concentrate the hydrogen peroxide by evaporating the water. It won't work above 30% as the heat decomposes more hydrogen peroxide than the proportion of water removed and you'd need a vacuum to properly distill H2O2 (which also has a high explosion risk). But you can easily get 20-25% H2O2 by just heating the diluted stuff at 70°C for 10 to 20 hours.
❤❤God bless you, Doctor N-BL! I just found an excellent source of oxalic acid yesterday at Ace hardware store. It is sold as a rust remover, right next to the HF acid for the same. They also sell h2so4 where I live ( same store even ). If you can't get these where you live but need some, "Blackhawk hardware (Ace)" online sells it. I'm sure you can even get 5 lbs of kmno4 online thru them, too, for just under 40 USD. I always love your exploration of science, and I've learned a lot through your channel. Thank you for every video. Failures sometimes are my favorite, even though I'm at first like "oh... he failed... not that video" at first, but then you're better than most. And your details on the science are soooo refreshing and seem to be giving others the notion to do the same, which I love to see. Please keep it up, and God bless you to your true name and your family.❤❤
hi, can you re-do this but with manganese sulfate ? manganese oxalate is 3 times less soluble than iron oxalate, and you wont run into problem of air oxidizing the subtracts . also I think there must be some way to recycle manganese oxalate.
I'm guessing the iron (ii) oxalate is at least partially a complex, which is why it is more strongly bound than the sulphate anion. But, I'm too lazy to go and dig out my undergrad textbooks to confirm this. Anyone??
Can you try sulphuric acid from ferrous sulphate oxidizing it to Fe³+ and precipitating it with copper oxide to make copper sulphate and use any method to obtain the sulphuric acid?
I wonder if there would be a way to set this up where the sulfuric acid falls to the bottom, due to its density, and can't react with the iron sulfate. I'm not a chemist, I'm a trucker, so idk if this is even theoretically possible
One day you should consider using your real voice for your videos, as it might be acoustically more pleasant to listen to ! But anyways, thank you very much ! You are still the master of the chemists around !
It's gotta be cheap for us fixed income types....OTOH I remember a mine adit in Arizona that was filled with melanterite (FeS04 hydrate from oxidized pyrite)
Maybe Copper Oxalate method failed because you used diluted chemicals and ambient temperature, as far as I remeber it is more preferable to use higher concentration of solutions and temperature to obtain bigger crystals.
You need to pass diamond vapor and chlorine over calcined wendigo bones at 600°C while reading the book of the dead. Be careful though as this is considered black chemistry and it is a forbidden art.
Iron(II) oxalate is insoluble. Iron(III) oxalate, on the opposite, is well soluble. Red rust contains mostly hydrated iron(III) oxide; black rust is a mixed Fe(II) and Fe(III) compound.
Astarion loves his photochemistry.
Alien digestion by-products?
just before this I was watching BG3 videos and I thought youtube glitched on me
I thought it was an ad and started looking for the skip button
Astarion legit caught me off guard and left me laughing for a good minute XD.
Brilliant
Praise the sun!
It's crazy to think how much my life has changed since first finding this channel. I have got married, had a kid, bought a house, paid it off, and had my 12th anniversary in the meantime. The videos have stayed at the same high quality. No annoying sponsorships, no over the top clickbait, just good repeatable information. Here's to another 15 years or so, Mr. Rage.
> bought a house, paid it off
> 15 years
😭
@@beefchicken It will never be easy to do ever again, and that's an absolute travesty.
Good on ya. You are on here and speak properly. So use your intelligence to organize your community, and teach chem to whoever will listen. We won't be able to afford decent housing soon, but that doesn't mean our future generations can't.
I don't care what your mother says about you, you sir are a genius, and do not let anyone tell you otherwise.
yeh this one is fairly impressive to me as well, hes really doin the chemistry here!!!
Awesome! Thanks for showing the stuff that doesn't work as well. Negative results are still results 😉
I thank you on behalf of the European amateur chemist (or wherever sulfuric acid is not available) for providing another alternative method to make sulfuric acid!
Sulphuric acid is Widely available in Europe. You must be in Netherlands or Belgium.
@@aga5897 No in either of these, but sulfuric acid in high conc. is banned in some places, and it is often hard to come by for amateur chemists even at lower conc. as I often heard people complained about it.
@@aga5897 It is often out of reach for amateurs as I often heard the struggles from other people. The US has it as a drain opener which is indeed a very luxurious thing to have.
15 % is available here.
@@experimental_chemistry 'Here' is only known to You.
feels kind of similar to how mathematicians insist on finding new ways of computing pi every now and then :D
Or "yet another proof of the Pythagorean Theorem".
Hahaha indeed
At first I was like, what? No, this is completely different, this is about amateur access.
But computing pi in dumb ways is kind of like amateur math, doing it just for fun, so yeah, it kind of is the same thing
Oxalic acid is a cheat code for mineral acids
Pretty much. It's also awsome for metal titration for the same reason.
can you use teraftalic acid instead ?
the power of kidney stone
@@ns-li4pr You should try, and report back here.
The least available part of this video was the sunlight lol.
England, eh?
whole world is cloudy lately@@nunyabisnass1141
To reduce the iron(III), just drop a piece of steel wool into the iron sulfate solution.
but then you'll consume the sulfuric acid and lower your yield.
@@NurdRage I meant just the iron sulfate solution - before adding the oxalic acid.
Just my thought.
For all the iron consumed from steel wool, same amount of carbon will settle and, again, reduce sulfuric acid@@RiehlScience
Doesnt the sulfuric acid oxidise iron ii oxalate to iron iii oxalate?
@NurdRage For really hard to filter stuff, I vacuum filter through a 10cm buchner funnel and filter paper with diatomacious earth. I really helps to add a round piece of course fiberglass cloth under the filter paper (slightly smaller than the filter paper): it adds lots of flow channels and also supports the filter paper so it won't blow through the holes in the funnel. You can also use plastic screen if it's resistant to whatever you're filtering. Just pre-wet the filter paper using water+DME and keep running the DME water until it runs clear. Rinse the flask and you're ready to go. Sorry for the late edit. One more thing that can really help: Seal the top of the funnel with a flexible film, like Saran wrap or even film from a condom (unlubricated 😉). It will compress the stuff above the filter and improve throughput. Caution: 14.7 PSI on a 10cm filter is (if I did the math right) almost 180 pounds of force! Wear safety glasses! And as I also found out, erlenmeyer flasks with a side arm are not always vacuum rated! Fume hood window & safety glasses saved me from my own ignorance/stupidity.
@NurdRage this
Just don't filter and distil directly.
centrifuge might help
He’s back boys!!
I was also playing around with the idea and found a way of making sulfuric acid from oxalic acid by heating oxalic acid together with regular magnesium sulfate epsom salt. when melted together it turned into a white sludgey liquid, which contained the sulfuric acid, which then could just be distilled off. Its also a really efficient method when making nitric acid, as potassium nitrate could just be mixed in with the dry oxalic acid and magnesium sulfate powder mixture. When heated the potassium nitrate reacted with the sulfuric acid and produced the nitric acid, which also could be distilled with ease.
Yeah, I actually thought about this method being possible a few years ago. It seems like it violates the “can’t make strong acid from weak acid” principle, but it actually doesn’t. It’s because that’s not the only force at play here it isn’t as simple as the oxalic acid protonating a sulfate ion and generating sulfuric acid. That kind of reaction is still unfavored. But you’re dealing with the power of Le Chatelier‘s principle. Oxalate is an unusual anion, due to how insoluble some of its salts are. And those salts are still mostly insoluble even in acidic conditions, which is rare. So the reaction is pushed forward by the mass action and formation of insoluble iron oxalate, NOT the protonation of sulfate. That still happens, but it needs the much stronger driving force of removing oxalate from the equation to overcome the unfavorable energy barrier.
Sulfate ion is not changed here. The driving force is a iron oxalate poor solubility. The “can’t make strong acid from weak acid” >>principle
@@WielkiKaleson that’s what I said. The sulfuric acid is formed as a result of the oxalate being insoluble. That force dominates even though what you would explicit to happen is nothing. Just a mixture of oxalate, sulfate, and hydrogen ions in solution.
Also for a “weak” acid oxalic acid is actually fairly acidic with a pKa of 1.25
@@spiderdude2099 Yes, of course you said. I just wanted to underline that although poor man's principles can be usefull, they often do not exist.
@@WielkiKaleson yeah, or they have a handful of specific exceptions.
@@spiderdude2099 In fact, in case of a solution, writing "H2SO4" can be missleading as it suggests such a species if floating around. On the other hand, although H2C2O4 is mainly not ionised, the ionised form is the player important here... So, I am not religious here.
The method using copper sulfate has worked out pretty well for me so far so I'm also puzzled by it not working out here. Admittedly it is a real pain to filter off the copper oxalate and it always will be. For me it usually does come out by letting it settle or running it through the frit several times. The only ways my procedure differs from yours is the fact that I'm using smaller amounts of reactants in less concentrated solutions and not heating anything. In fact the oxalic acid gets pretty cool upon dissolving so it's usually below room temp. The lower concentration of reactants also makes the suspension of copper oxalate thinner which might help it settle.
Another thing I want to mention is that a similar process can be done using sodium bisulfate and hydrochloric acid. By adding finely powdered NaHSO4 to concentrated HCl it will react to form sodium chloride which is sparsely soluble in concentrated HCl. It doesn't look like a lot is happening but upon reacting these in hot solution, cooling, filtering and distilling one actually obtains quite a bit of sulfuric acid. The yield sure isn't too high but the nice thing is that you get your unreacted starting materials back. Unreacted HCl just distills off and NaHSO4 precipitates out while concentrating the sulfuric acid. For lack of a better alternative this is usually my go to route.
Furthermore there's this which i haven't yet tried myself: www.sciencemadness.org/talk/viewthread.php?tid=79548
(there should be a url there, i hope yt plays along)
Also just let my say that you made one hell of an amazing video again which is of great value to the amateur chemistry community. You never seem to disappoint. Thanks!
I can't believe you could post an outside link. RUclips have deleted so many of my comments with links I don't even consider it possible anymore. I wonder what it is that make some links allowed and most not.
I am unsure about the practical usefulness of this process, but it is very elegant and smart, nice job. Your videos have taught me a lot and this one doesn't disappoint either.
6:07 I totally thought this fine NurdRage video had been interrupted at the BEST PART by one of those stupid game ads. 😂
I wonder if chilling the copper sulfate solution prior to oxalate addition would slow crystal growth and thus create "bulkier" particulates that would be able to be filtered on at least a frit if not even a paper filter.
Or perhaps a known flocculating agent?
Best chemist on youtube
i hope you'll show the same method for making nitric acid as well, since magnesium nitrate does work for making nitric acid and it's much easier to distill than sulfuric acid it's the best method for making nitric acid requiring no high temperatures or expensive sulfuric acid
I bet you are unaware of the impressive number of people that became chemists fom your inspiration just by simply helping me pave my way to it since I made sure to perpetrate the passion for it and I'm pretty confident I'm not the only one.
Following this channel since 1999. Great stuff as always.
If NurdRage emerges out of his Nurd Hole without a new recipe for sulfuric acid, it means another six weeks of winter
Sweet. Great to see more accessible syntheses.
All through this video, I was thinking about the big bag of copper sulphate out in the shed... so thanks for answering my inevitable question without me even having to ask it. :)
Благодарим ви!
Thank you so much!
Ferrous sulfate solution should be a nice seafoam green color. I noticed your ferrous oxidize when your water was introduced. If you can force the orp to a double digit number you can keep your Fe2 from turning into Fe3( your pH should be rather low especially after OxAcd so you avoid the risk of dropping out fe3 at pH3.6) the reason i mention this is that Fe3 is soluble in the presence of oxalate. So your fe3 is inadvertently taking up oxalate . Not sure how that will affect your yeild but it keeps your oxalate oxalic acid in equilibrium perhaps decreasing your yeild. Just a thought.
Just finished the vid nevermind
Technical grade ferrous sulfate contains a significant proportion of ferric sulfate already before dissolved.
Potentially the pore size of the is larger than that used by other amatuers.
It's always interesting to hear more examples of things that go against what you're taught in highschool/undergraduate chemistry classes!
Copper oxalate simply needs a good centrifuge, IMO.
Just my thought.
That's what I was thinking.
You might not even need a high-powered (expensive) one. Copper II Oxalate has a density of 6.57 g/cm3.
Presumably you could DIY a centrifuge to separate something more than 6 times denser than water, even if it is in molecule-fine particles.
Just be careful to balance!
Most centrifuges do 10 ml or so. Unless you've got a grad student/peon this wouldn't be fun
Oil flywheel centrifuge should work. the big heavy kind they use for biodiesel.
If size is an issue then maybe a lawn mower centrifuge? I just bought one so it came to mind.
6:00 As a reducing agent you can use regular iron wool. It reduces Fe3+ to Fe2+ while going in solution as Fe2+, gives a purer product and can be easily filtered off.
A slightly easier, and possibly more time saving way to photodecompose the iron oxalate would be to use a UV lamp. Those can be fairly cheap, only run on similarly cheap electrical power, and are sometimes even more powerful than the UV you get from exposure to the sun, especially if you place the beaker directly under it and blast it for a while up close and in a contained area.
Maybe a wick siphon would work on your copper sulfate slurry. It works for fine particles in muddy water.
Excellent! after googling I found that iron sulphate heptahydrate is = ferrous sulphate, te one easy to get that I use on the garden. Oxalic acid is also easy to get as wood bleacher.
I do enjoy the clarification of parallel methods that may (or may not) work. It's fascinating how transition metals with supposedly equivalent behaviors end up being entirely different when you go to try the method. Should the metal oxylate form? Sure thing. Does it? Probably. Can you separate it? Not at all, yes, and maybe.
This was a chemical reaction I'm curious about, never knew they was a easier way to recover sulfuric acid using oxalic acid. When salts like sodium or potassium sulfate are form they really difficult to make sulfuric acid unless using a way more stronger acid then sulfuric acid, or a electrolysis that involves to much current. Oxalic acid do form alot of insoluble metal salts... It's a miracle that we can do this, this why I love this reaction.
Another side note, could have tried less water when using copper sulfate, I could have produce a thicker crystal of copper oxalate, then later on dilute it down if required. It really makes us curious weither the yield was good.
Don't they usually use some polyaluminates to flocculate more effectively?
great vid tho.
I really thought the magnesium would work; ion radii are similar so you'd think it would just electrostatically sort of work out... clearly more going on of course :)
I feel like if you could continuously filter the precipitate out the magnesium yield would go up. Like use a cheap aquarium pump to cycle it through a filter. Might take longer but bulk processing "hands off" is still pretty good.
About copper oxalate. You could try some classic ways to get bigger particles. For example slow addition and performing this reaction in hot solution to promote slower crystallisation. Those are at least from the top of my head. Or you could also try filtering through a layer of celite if you have some, maybe it will be able to stop the precipitate. Anyway I now want to see the yield of H2SO4 from this. 😅
If oxalic acid is strong enough to displace H2SO4 from FeSO4, could this be modified to work with a nitrate salt (say, CuNO3) that would be rendered insoluble upon reaction with oxalic acid and produce HNO3? Im aware it's probably far more efficient to use the NaHSO4 and KNO3 distillation method, but it does make me curious if its possible on a theoretical level. Another absolutely genius, awesome video!
Oxalic acid solution added to calcium nitrate solution precipitates calcium oxalate and yields dilute nitric acid. Let precipitate settle, decant, filter, distill. This also works with CuNO3
@@jbone877 Very interesting. Thanks for the information. I had a hunch it would work but i was curious if anyone could confirm it. Oxalic acid is incredibly capable for a weak organic acid. It also works great for cleaning MnO2 and FeCl3 stains which are a pain to deal with (from personal experience).
@@keithm5378 With a pKa around 1.5, oxalic acid isn't actually that much of a "weak" acid, compared to for example citric acid with 3.1
@@stefangadshijew1682 This is true, I suppose I should have clarified that I meant the technical term "weak acid" (an acid that does not fully ionize in solution). I'm still a noob amateur chemist learning the ropes, but it's my understanding that as a general rule, weak acids cannot displace strong mineral acids (H2SO4, HNO3, HCl, HBr, HF, HI is a bit of a weird case though) from their respective salts in any meaningful amount. For example, you can't make HCl from adding glacial acetic acid to table salt, but it absolutely works with heating a mixture of salt and bisulfate and bubbling the gas into water with a funnel trap as NurdRage has demonstrated, and i have personally made HCl that way.
I know this rule doesn't always apply in every situation though because I've read you can make the strong, volatile mineral acids from the action of hot phosphoric acid, technically a "weak acid", on their respective salts, you just have to be mindful of the fact hot H3PO4 etches glass at those temps.
@@keithm5378 Hey there! :)
The "rule" of "strong acids liberate weak acids out of their salts" isn't really a rule. The rules at play here is the law of mass action and the principle of La Chatelier.
You've got an equilibrium between two acids that favors the formation of the weak acid. But then you also have other equilibria or non-equilibrium-reactions that can shift the equilibrium to the product side.
If you generate HCl with H2SO4, you are also generating the stronger acid with the weaker acid. (pKa -6 and -2 respectively).
But since you are distilling off the HCl, there will always be new H2SO4 and NaCl consumed and the reaction goes to completion.
Those precipitation reactions are exactly analogolous.
Always love these videos of making reagents from potential waste products from other reactions. 😁
If using CuSO4, I've had good results freezing the copper oxalate suspension prior to filtration. Upon thawing, the majority of the precipitate settles to the bottom of the reaction vessel in a relatively homogenous cake, making decanting viable prior to filtration.
This reminds me how I once made (rather dirty) HBr without distillation. I only had KBr as a source of bromide, so I first mixed it with calculated amount ZnSO4 and using fractional crystallization separated K2Zn(SO4)2, then used oxalic acid to liberate HBr from the remaining ZnBr2. Rather absurd process, but it worked.
Excellent. Thank you
NurdRage is Da Boss !
One way to purify/concentrate Sulphuric is to boil the hell out of it until the fumes become thick.
Then add a splash of 3% H2O2 if it's brown.
Amazingly that actually works with no dramas, in my case at least.
someday i'm going to assemble all my separate sulfuric acid videos into a "complete guide" video. :)
@@NurdRage Question: do you ever get contact from the SM folks from back in Your days there?
I did, saying they missed me.
That's like saying they missed a hole in the head, which was a bit odd.
Not really, and its been so long that i'm sure more than half the people i once knew likely moved on. so even if i did come back there wouldn't be anyone to recognize me.
@@NurdRage Same here - there was a time, stuff moves on - Evolution i guess.
You made a Smart choice about the Video thing.
Legend !
Hmm...your username seems familiar, I think I came across a user "aga" in SM when I was researching the distillation of Ethanol.
Given that you already have green vitriol one can simply extract the oil of vitriol by destillation, Sir!
If you mean dry distillation of the sulfate salts this is viable (it has been done for centuries) but involves very high temperatures (>600°C), it can't be done in ordinary borosilicate lab glass, and it is very dangerous.
I wonder if a centrifuge would work to separate copper oxalate
It would, but centrifuges of any decent capacity are outside the reach of amateur chemists.
I'm already subscribed. Waiting on the nitric acid video.
You are very, very wonderful. I have learned a lot and a lot from you. I want to ask for your help. Can you make a video about the synthesis of sodium ethyl sulfate and then the synthesis of nitreethane from it?
Calcium sulfate would be a good one to try
Yes, it would be interesting, but it's probably very slow reaction due to the very low solubility of CaSO4.
@@user255 yeah that’s true
You can also try bubbling hydrogen sulfide into a solution of copper sulfate; as a result, copper sulfide precipitates, leaving sulfuric acid in the solution. Hydrogen sulfide can be produced by heating sulfur with paraffin.
Hydrogen sulfide is deftly toxic, not something amateurs should be handling
Oh and the stench! Can’t have neighbors or they will report you to DEA with that procedure!
@@NurdRagewell, experienced amateurs with a proper setup can definitely handle hydrogen sulfide. It's toxic, more than chlorine and nearly as much as hydrogen cyanide, but the smell is so disgusting and strong that anyone would notice being exposed and evacuate the area long before the dose becomes unsafe. But if it can be avoided it should definitely be avoided.
@@lagrangiankid378 Not true! Surprisingly, in high concentrations H2S becomes odorless.
@@user255 Yes, I know that, it's odorless at more than 100 ppm due to desensitization, but long before the concentration rises to dangerous levels you notice its presence pretty evidently and this is enough to evacuate, wear a respirator or take any action.
that clip of Astarion yelling about sun was so unexpected i nearly choked on my tea.
From a molecular bio approach, I think centrifugation is probably the best way to seperate the milk of coppernisia you made, though this requires a centrifuge. If you have one already this might be worth exploring
You mentioned acetic acid off hand, and that made me wonder anout using perocetic acid for making rust, instead of going the ferous chloride route in a previous video, for rust. I know rhe advantage of HCl is that it works faster, but I've had visually satisfying results using 30% acetoc acid with scrap steel, then adding the peroxide to oxidise it later.
Very cool!
I have been watching your videos for so long it's ridiculous; I just have a quick comment on a possibility for an improvement in this one. Would there be any possibility of improvement in the copper method using a very fine Celite? Or rather more specifically, would you be able to separate an extra fine celite powder from the distillate and then be able to use the resulting solution?
Unfortunately instead of my original college degree being chemistry (like 7 years ago), I decided to go with Finance, so I truly don't know if there's any major issues with this thought, but if you or anyone else cares to respond, I would be thrilled to gain any knowledge y'all have about this process!! =)
I think that equimolar mixture of potassium sulfate and sodium sulfate might also work, as NaKC2O4 is also insoluble in water.
I wonder if HF with Calcium salts would also work due to the extreme insolubility of CaF2.
Tbh I'd really rather not find out 😅
As cheap as off grid solar is nowadays , I don't see any downside to using it for a continuous electrolytic chemical factory , for producing all sorts of useful stuff , like chloratea , perchloratea , acids , whatever .
You can have a shed or garage full of Pauling furnaces running 24 / 7 . Sure they are inefficient , but , once you have your PV setup , the rest is just childs play and it can run indefinitely courtesy of the sun , assuming you have enough storage capacity to run that long , and , enough panels to keep the storage bank topped off .
Pretty sure you are some kind of genius
Thank you ❤
Oxalic acid also increases the absorption of Cr(lll), in the body, among other things.
Centrifuging to speed up the sedimentation of the copper oxalate? Freezing the solution with the hope the ice crystals will compact the copper oxalate particles?
Será que não dá pra fazer ácido sulfúrico com ácido sulfamico + ácido nítrico??
You think that there is a way starting from sulfamic acid? It is strong, cheap and upon boiling hydrolyses to ammonium hydrosulfate…
Can difficult filtrations be tackled by centrifugal methods ? Not available to most but I’m sure I could build something IF it would work.
Do you think aluminium sulfate could be used instead of ferrous sulfate. It is also insoluble in water, so it should be nearly the same reaction, or is there something more to ir
and what is the best way to get nitric acid to make the oxalic acid if you don't have sulfuric acid or oxalic acid?
Best chanel. 😊
Engaging to combat YT censorship against Chemistry!
Citric acid also reduces ferric ion in direct sunlight
Does this mean ebonizing wood with iron (II) sulfate also produces small amounts of sulfuric acid in the wood after the iron tannate complex forms? I know you say it doesn't work with other acids but if they weren't reacting there wouldn't be tons of black complex crashing out and dyeing the wood.
How does the yield compare to dry-distilling the Iron Sulphate directly, like back in the days of alchemy? Suppose I bought a 50lb sack of the stuff because it's not particularly expensive, and making an iron retort isn't a problem.
u could try to build a selfmade centrifuge with plastic bottles on each side and try to push the copper oxalate down
Could you generate H2SO4 by bubbling SO2 into H2O2 ?
Yes, that works - to a certain extent: because the reaction mixture gets hot (so it needs to be cooled down well), and the hotter it gets the less SO2 dissolves and reacts.
Yea i did it but since i cant get more than 6% h2o2 it wasnt worth my time
@@ae-bd5grsimply concentrate the hydrogen peroxide by evaporating the water. It won't work above 30% as the heat decomposes more hydrogen peroxide than the proportion of water removed and you'd need a vacuum to properly distill H2O2 (which also has a high explosion risk). But you can easily get 20-25% H2O2 by just heating the diluted stuff at 70°C for 10 to 20 hours.
❤❤God bless you, Doctor N-BL! I just found an excellent source of oxalic acid yesterday at Ace hardware store. It is sold as a rust remover, right next to the HF acid for the same. They also sell h2so4 where I live ( same store even ). If you can't get these where you live but need some, "Blackhawk hardware (Ace)" online sells it. I'm sure you can even get 5 lbs of kmno4 online thru them, too, for just under 40 USD. I always love your exploration of science, and I've learned a lot through your channel. Thank you for every video. Failures sometimes are my favorite, even though I'm at first like "oh... he failed... not that video" at first, but then you're better than most. And your details on the science are soooo refreshing and seem to be giving others the notion to do the same, which I love to see. Please keep it up, and God bless you to your true name and your family.❤❤
Would alum help the copper oxalate settle?
Gotta love me some good reducing agents ;)
Could there be a use for extremely finely divided copper oxalate?
hi, can you re-do this but with manganese sulfate ? manganese oxalate is 3 times less soluble than iron oxalate, and you wont run into problem of air oxidizing the subtracts . also I think there must be some way to recycle manganese oxalate.
Is the yield of the se reactions Better than electrolysis of copper sulfate?
Can we make weak nitric acid from calcium nitrate and oxalic acid? I suspect that the low solubility of calcium oxalate should permit this to work.
I'm guessing the iron (ii) oxalate is at least partially a complex, which is why it is more strongly bound than the sulphate anion. But, I'm too lazy to go and dig out my undergrad textbooks to confirm this. Anyone??
I just looked on Wikipedia, and it's a coordination polymer with the oxalate bridging between two irons, hence the stability and low solubility.
Love from India ❤❤❤
could you do this with like... fumaric acid in acetone with sodium sulfate? would that be cheaper?
Nitric acid seems really expensive. Is it worth the time and inputs to make it in my own lab instead of buying it?
Have you tried centrifuging the copper oxalate?
Can you try sulphuric acid from ferrous sulphate oxidizing it to Fe³+ and precipitating it with copper oxide to make copper sulphate and use any method to obtain the sulphuric acid?
Oxalic acid? Fascinating. Get out your kiwifruit skins and rhubarb stalks! We're making sulfuric acid!
Rhubarb leaves*
Interesting! Is it possible to produce other strong acids this way as well?
yes, it can make nitric acid
@@NurdRage 😉😄👍
I wonder if there would be a way to set this up where the sulfuric acid falls to the bottom, due to its density, and can't react with the iron sulfate. I'm not a chemist, I'm a trucker, so idk if this is even theoretically possible
By centrifugation you can separate things by density. But sulfuric acid is fully miscible with water so this would not work at all.
One day you should consider using your real voice for your videos, as it might be acoustically more pleasant to listen to ! But anyways, thank you very much ! You are still the master of the chemists around !
For when you really need H2SO4😂
hi 1 method of separating the copper is to use a centrifuge
It's gotta be cheap for us fixed income types....OTOH I remember a mine adit in Arizona that was filled with melanterite (FeS04 hydrate from oxidized pyrite)
Maybe Copper Oxalate method failed because you used diluted chemicals and ambient temperature, as far as I remeber it is more preferable to use higher concentration of solutions and temperature to obtain bigger crystals.
Free sun is a giant plus :)
Filter paper for the copper?
How to Nutrilize nitric acid ?
Hello how r u sir how to make Diamond chloride making the video
You need transparent aluminum and unobtanium, both very expensive reagents, basically impossible to get.
Reacting diamond with chlorine would give various chlorocarbons, like carbon tetrachloride.
You need to pass diamond vapor and chlorine over calcined wendigo bones at 600°C while reading the book of the dead.
Be careful though as this is considered black chemistry and it is a forbidden art.
I don't get it. If iron oxalate is insoluble why oxalic acid used to dissolve rust?
Iron(II) oxalate is insoluble. Iron(III) oxalate, on the opposite, is well soluble. Red rust contains mostly hydrated iron(III) oxide; black rust is a mixed Fe(II) and Fe(III) compound.
Heating FeSO4 could be changed to SO3 gas. yield is 100%.