PillaDoubleG Posted February 2 Share Posted February 2 I've stated before that I don't want to use nitric acid to produce nitrate salts, for multiple reasons: 1. I'm not a qualified chemist, and I am fairly scared to work with any type of very pure acid. I know that if you wear the proper gloves and eye protection there really isn't much that the acid could do to you... but still. 2. Making conc. nitric acid would require me to buy an entire distillation setup, and probably some other stuff. I do in fact have the money for it, I'm just a cheapskate. Now, my plan of synthesizing BaNO3 goes something like this... For context, my starting point is barium sulfate since I can't get any other barium salt. BaSO4 => BaCO3 (this part I need help with) The rest of the process I have figured out... BaCO3 + HCl => BaCl2 + CO2 + H2O BaCl2 + NaNO3 => Ba(NO₃)₂ + NaCl These reactions aren't balanced, but oh well... The sodium nitrate process will go something like this: NH4NO3 + NaHCO3 => NH4HCO3 + NaNO3 The ammonium bicarbonate decomposes at around 40C (producing ammonia gas unfortunately), which leaves only the sodium nitrate in solution, which can be crystalized out. Btw I took this reaction from TheCanadianChemist. The part that I haven't figured out yet is the BaSO4 => BaCO3. My original idea was to react the BS with carbonic acid (H2CO3), which would not work in so many ways... But even if it somehow did, it would make BaCO3 + H2SO4, and BaCO3 decomposes in sulfuric acid, so a dead end there. I also thought about BaSO4 + Na2CO3 => BaCO3 + Na2SO4, but BS is insoluble in water, only soluble in sulfuric acid... Then I decided to ask my chemistry teacher if she had any ideas, and she gave me this proposal: BaSO4 + CO2 => BaCO3 + SO3, producing the CO2 with vinegar and baking soda, capturing the CO2 and driving it into a container with barium sulfate in it. I thought this was good at first, but multiple problems arise again... SO3 is toxic, which is no Bueno again. And I would have no way of knowing if the gas I'm looking at is CO2 or SO3... My teacher said that it doesn't matter that the BS is a solid and that CO2 is a gas, and that they will still react... I don't really now if I believe her though. This is all of the research I have done so far... I really have no idea where else to look for for help. Tried to make this as detailed as possible so other people don't waste their time. Feel free to ask me any questions in case I forgot to mention something, I will be taking any suggestions or help you send my way. Once again, thank you APC Link to comment Share on other sites More sharing options...
CountZero Posted February 2 Share Posted February 2 The usual method is to react the barium sulfate with carbon at high temperature. This gives you BaS, that can be reacted with HCl. I would try to look harder for a pottery supplier, or make friends with a potter. Link to comment Share on other sites More sharing options...
PillaDoubleG Posted February 2 Author Share Posted February 2 (edited) 1 hour ago, CountZero said: The usual method is to react the barium sulfate with carbon at high temperature. This gives you BaS, that can be reacted with HCl. I would try to look harder for a pottery supplier, or make friends with a potter. Thanks for the advice, 2 questions tho... How high of a temperature are we talking? Is it in the metal melting temperatures, or lower? And how do I get rid of the H2S that's produced? That's even more toxic than the SO3 one!!! Oh and about the pottery supplier thing, if the chemical you're looking for isn't really used commercially, there is a 95% you will not be able to find it ANYWHERE. I will keep searching, in case I find something Edited February 2 by PillaDoubleG Link to comment Share on other sites More sharing options...
Arthur Posted February 3 Share Posted February 3 I can find two suppliers for barium nitrate, online but not in USA. Sometimes you have to search the web. Link to comment Share on other sites More sharing options...
FrankRizzo Posted February 3 Share Posted February 3 Pilla - Which country are you loacted? Link to comment Share on other sites More sharing options...
cmjlab Posted February 3 Share Posted February 3 Couple Thoughts: The process you describe is long, complicated, and partially theoretical. Even if you do complete parts of the process, id be worried about sodium contamination or actual yields of final product being worth the time and expense. Whereas a simple distillation setup will produce adequate quality Nitric Acid to make Barium Nitrate and is far less involved of a process. 2. Barium salts are toxic too (minus the sulfate), along with lots of other pyro chems, and if you don't know how to make a scrubber / gas trap to capture toxic gasses then I'd be wary of longer processes (as described in the original post). I'm not saying you're way won't work, nor do I know what you have vs. need to acquire for any of the methods described above - so I just tossed in my thoughts. Im also not a college edjumahcated chemist like some other folks here...... But I do have Google and YouTube! 😁 Link to comment Share on other sites More sharing options...
CountZero Posted February 3 Share Posted February 3 (edited) >How high of a temperature are we talking? I think at least 800C It seems you can use CO also(at these temperature), possibly CO2 also but I did not find a reference. It is used and pretty common. https://www.axner.com/barium-carbonate-german.aspx Finding a local source is good, shipping fancy dirt gets expensive. Edited February 3 by CountZero Link to comment Share on other sites More sharing options...
CountZero Posted February 3 Share Posted February 3 Also, even if you get barium carbonate it will probably have some sulfide as impurity so you will get some H2S anyway. Link to comment Share on other sites More sharing options...
PillaDoubleG Posted February 3 Author Share Posted February 3 11 hours ago, Arthur said: I can find two suppliers for barium nitrate, online but not in USA. Sometimes you have to search the web. I have, but absolutely no pyro supply companies exist in Serbia. Even if you found some in Europe, it doesn't guarantee anything because Serbia's not in the EU. All of the pyro supply companies I have found shipped to EU only. 9 hours ago, FrankRizzo said: Pilla - Which country are you loacted? Serbia, I apologize for forgetting to mention that in my original post. For some reason I can't find any local pottery or ceramic companies that sell strontium or barium carbonate. 8 hours ago, cmjlab said: Couple Thoughts: The process you describe is long, complicated, and partially theoretical. Even if you do complete parts of the process, id be worried about sodium contamination or actual yields of final product being worth the time and expense. Whereas a simple distillation setup will produce adequate quality Nitric Acid to make Barium Nitrate and is far less involved of a process. Yeah I'm well aware that the process is long, probably a waste of time and money as well... But this whole process is my absolute last backup plan, if I don't manage to find a single other source of barium. I will maybe buy a distillation setup in the future and all the other stuff required, once I get a job 2 hours ago, CountZero said: >How high of a temperature are we talking? I think at least 800C https://www.axner.com/barium-carbonate-german.aspx Finding a local source is good, shipping fancy dirt gets expensive. Unfortunately, I cant get a temperature even near that, but that website does actually offer shipping to Serbia, thank you for sending that to me! The salts are also decently cheap. I will check out what the site further has to offer. 1 hour ago, CountZero said: Also, even if you get barium carbonate it will probably have some sulfide as impurity so you will get some H2S anyway. That is a possibility, thing is: BaCO3 isn't soluble in water, but BaS is decently soluble. So I could probably just put in the BaCO3 in some hot water and all of the impurities would just dissolve. There could be some insoluble salts there, but I think the chance of that is pretty low. Sorry for answering the questions fairly late, time zones... ya' know... Link to comment Share on other sites More sharing options...
PillaDoubleG Posted February 3 Author Share Posted February 3 (edited) 3 hours ago, CountZero said: https://www.axner.com/barium-carbonate-german.aspx Finding a local source is good, shipping fancy dirt gets expensive. Nevermind actually, the shipping for 10 pounds of SrCO3 and BaCO3 is $124... YIKES I will keep searching for other websites tho!!! Edited February 3 by PillaDoubleG Link to comment Share on other sites More sharing options...
AustralianPyromaniac Posted February 5 Share Posted February 5 This would be easier if you could start with BaCO3. I think there also may be some misconception about some of your reactions. None of the products are insoluble and the products are therefor hard to separate. I also disagree with your chemistry teacher regarding the bubbling CO2. I don’t think it would work with an insoluble compound. I could be wrong. What nitrate salts can you get and are widely available for you. You’ve used ammonium nitrate, is that your best option in Serbia? What other nitrates can you get. N.B. I think it would be easiest if you could distill nitric acid. Or if you could get sulphuric acid I could think of some pathways with that. But I assume you can’t get sulphuric. —- Putting the sulphate in a metal container and putting that in a camp fire to generate the required temperature would probably be the best approach. It may eat the container, would have to try it. I have been thinking about this question for the last two days and have come up with no good solutions. I haven’t seen anyone else propose anything great, because don’t think there is any good approach. I’d once again recommend making barium chlorate by electrolysis. On 2/2/2024 at 8:21 PM, PillaDoubleG said: I've stated before that I don't want to use nitric acid to produce nitrate salts, for multiple reasons: 1. I'm not a qualified chemist, and I am fairly scared to work with any type of very pure acid. I know that if you wear the proper gloves and eye protection there really isn't much that the acid could do to you... but still. 2. Making conc. nitric acid would require me to buy an entire distillation setup, and probably some other stuff. I do in fact have the money for it, I'm just a cheapskate. Now, my plan of synthesizing BaNO3 goes something like this... For context, my starting point is barium sulfate since I can't get any other barium salt. BaSO4 => BaCO3 (this part I need help with) The rest of the process I have figured out... BaCO3 + HCl => BaCl2 + CO2 + H2O BaCl2 + NaNO3 => Ba(NO₃)₂ + NaCl These reactions aren't balanced, but oh well... The sodium nitrate process will go something like this: NH4NO3 + NaHCO3 => NH4HCO3 + NaNO3 The ammonium bicarbonate decomposes at around 40C (producing ammonia gas unfortunately), which leaves only the sodium nitrate in solution, which can be crystalized out. Btw I took this reaction from TheCanadianChemist. The part that I haven't figured out yet is the BaSO4 => BaCO3. My original idea was to react the BS with carbonic acid (H2CO3), which would not work in so many ways... But even if it somehow did, it would make BaCO3 + H2SO4, and BaCO3 decomposes in sulfuric acid, so a dead end there. I also thought about BaSO4 + Na2CO3 => BaCO3 + Na2SO4, but BS is insoluble in water, only soluble in sulfuric acid... Then I decided to ask my chemistry teacher if she had any ideas, and she gave me this proposal: BaSO4 + CO2 => BaCO3 + SO3, producing the CO2 with vinegar and baking soda, capturing the CO2 and driving it into a container with barium sulfate in it. I thought this was good at first, but multiple problems arise again... SO3 is toxic, which is no Bueno again. And I would have no way of knowing if the gas I'm looking at is CO2 or SO3... My teacher said that it doesn't matter that the BS is a solid and that CO2 is a gas, and that they will still react... I don't really now if I believe her though. This is all of the research I have done so far... I really have no idea where else to look for for help. Tried to make this as detailed as possible so other people don't waste their time. Feel free to ask me any questions in case I forgot to mention something, I will be taking any suggestions or help you send my way. Once again, thank you APC Link to comment Share on other sites More sharing options...
FrankRizzo Posted February 5 Share Posted February 5 2 hours ago, AustralianPyromaniac said: I’d once again recommend making barium chlorate by electrolysis. None of his available barium salts are soluble. How would barium chlorate be easier? Link to comment Share on other sites More sharing options...
AustralianPyromaniac Posted February 6 Share Posted February 6 10 hours ago, FrankRizzo said: None of his available barium salts are soluble. How would barium chlorate be easier? It would eliminate that final double displacement to the barium nitrate, which is the worst step of the process. I think it’s also a better use of limited barium, and one that I’ve proposed in the past for OTC pyrotechnics. Link to comment Share on other sites More sharing options...
CountZero Posted February 6 Share Posted February 6 I once made a small test going from barium carbonate to barium chloride with HCl and double displacement with calcium nitrate. It works, but takes some time and the yield is not 100% also for strontium nitrate I don't think it is a viable way. Link to comment Share on other sites More sharing options...
AustralianPyromaniac Posted February 6 Share Posted February 6 HCl can be used to turn any carbonate into a chloride. Including strontium. The yield is close to 100%. Strontium chloride is hydroscopic and thus hard to dry. Also it’s more contaminated than barium carbonate, which releases hydrogen sulphide during the reaction. Link to comment Share on other sites More sharing options...
CountZero Posted February 6 Share Posted February 6 I was thinking about the last step with double displacement since strontium nitrate is much more soluble than barium nitrate I think it will be harder to separate from for instance calcium chloride. Link to comment Share on other sites More sharing options...
PillaDoubleG Posted February 6 Author Share Posted February 6 23 hours ago, AustralianPyromaniac said: This would be easier if you could start with BaCO3. I think there also may be some misconception about some of your reactions. None of the products are insoluble and the products are therefor hard to separate. I also disagree with your chemistry teacher regarding the bubbling CO2. I don’t think it would work with an insoluble compound. I could be wrong. What nitrate salts can you get and are widely available for you. You’ve used ammonium nitrate, is that your best option in Serbia? What other nitrates can you get. N.B. I think it would be easiest if you could distill nitric acid. Or if you could get sulphuric acid I could think of some pathways with that. But I assume you can’t get sulphuric. I’d once again recommend making barium chlorate by electrolysis. It would be easier, and I could possibly get barium carbonate, but the shipping would bankrupt me... There is a actually a decently wide variety of nitrate salts. You have: ammonium, potassium, magnesium, calcium, and probably a few others. The only ones that are useful are potassium and ammonium tho. It would 100% be the easiest to distill nitric acid, and I can actually get the chemicals and the equipment for it. Sulfuric acid can be readily bought here, in a low concentration, but still. I am really considering the electrolysis option right now, but another problem arises, what binder do I use? I see people always make the star with shellac, which i can't get. Would dextrin work? I could get some other binders possibly, SGRS is one. And as frank mentioned, i would still somehow need to get to barium chloride. But it's MAYBE possible. 6 hours ago, CountZero said: I once made a small test going from barium carbonate to barium chloride with HCl and double displacement with calcium nitrate. It works, but takes some time and the yield is not 100% also for strontium nitrate I don't think it is a viable way. Was your product impure in any way? Using sodium nitrate, my original plan, the final product would be impure because of the sodium, and I don't really see it giving off a nice green color. Link to comment Share on other sites More sharing options...
Skyboomer Posted February 6 Share Posted February 6 Fireworks Cookbook has Barium Nitrate for $6.50 a pound (?) last time I checked. Unless you’re just stuck on making it yourself, I’d just buy it. It’s cheap. Link to comment Share on other sites More sharing options...
FrankRizzo Posted February 6 Share Posted February 6 11 hours ago, AustralianPyromaniac said: It would eliminate that final double displacement to the barium nitrate, which is the worst step of the process. I think it’s also a better use of limited barium, and one that I’ve proposed in the past for OTC pyrotechnics. He doesn't have access to a water soluble barium salt. Electrolysis is a non-starter. Link to comment Share on other sites More sharing options...
AustralianPyromaniac Posted February 6 Share Posted February 6 1 hour ago, FrankRizzo said: He doesn't have access to a water soluble barium salt. Electrolysis is a non-starter. This was referencing a previous convo with OP which I recommended the use of barium chlorate under a post asking for similar advice about making the nitrate. It’s not really in context of this question, as you say a soluble salt is needed first. But it was just a small part of my post linking back to what I had said in the past, as a reminder, which I think he would have understood it to be. Link to comment Share on other sites More sharing options...
AustralianPyromaniac Posted February 6 Share Posted February 6 The only approach for this problem I have come up with would be to mix the barium sulphate in a blender with charcoal in large excess. Then place this mixture in a paint can and heat in a fire for some time, the same way charcoal is made, with vent holes. This should yield the sulphide + CO, which would burn to CO2 in the fire. This should not eat through the metal tin or release toxic fumes. Once this is done, dissolve the resultant mixture in boiling water and filter to remove impurities. The solution which is produced should be of barium sulphide (BaS). This is the answer to the initial question regarding how to get it out of the sulphate form. Although you asked to get it to the carbonate, this is nearly the same. To turn to nitrate, a few approaches can be taken. 1) Mix with balanced amount of ammonium nitrate and bring solution to boil, liberating H2S + NH3 gas by decomp of ammonium sulphide. Solution which remains is barium nitrate and water. The gas released must be scrubbed. (This reaction I am not 100% sure is possible) 2) Mix with magnesium or calcium nitrate to yield a precipitate of poorly soluble Mg/Ca sulphide, and a solution of barium nitrate. 3) Mix with urea nitrate to yield urea sulphide (which may not exist and solubility unknown) unsure if this compound exists but if it is insoluble then it would be useful 4) Mix with Cu/Fe nitrate to yield precipitate of insoluble sulphide and barium nitrate. Cu/Fe can be recovered by work up then reaction with less noble metals 5) Mix with Na/K/NH4 nitrate and chill to possibly precipitate Ba(NO3)2 leaving the sulphide in solution. Solubility unclear. 6) Mix with HCl to produce the chloride for electrolysis to chlorate yielding H2S which escapes solution and must be scrubbed. —- None of these reactions are ideal. But much simpler than the pathways you proposed. What makes these reactions work is the solubility of the salts involved. You’ll learn in chemistry that the solubility numbers and info given on the internet are often not correct and are misquoted. This can really stuff up calculations. I am currently in Bosnia of all places, and away from all my books and my laptop in Australia, so I have taken values from the internet, but they are often wrong. And some numbers contradict others. Some homework, look up “CRC Handbook of Chemistry and Physics PDF” and download it. Or maybe you can borrow a copy from your local library. You’ll find exact and very reliable values for the solubility of these salts in that book, if you can post them here we’d be able to help you more, and I’d be able to check my work. The ones I am not sure on are the sulphide salts of Mg/Ca/NH4/K/Na. Specifying at STP is enough, but you’ll find solubility across full temp range. None of the above reactions are great pathways and not really what you asked for, as I said earlier, there is no good way to do this. But it should help a bit on what you may want to do. AP. 1 Link to comment Share on other sites More sharing options...
Powderman Posted February 9 Share Posted February 9 If source of carbonate would be found this one may help skip the nitric acid: boiling solution of NH4NO3 with BaCO3 works. NH3 and CO2 escape as gas. Link to comment Share on other sites More sharing options...
TXpyro Posted February 13 Share Posted February 13 Just buy some barium nitrate. Link to comment Share on other sites More sharing options...
PillaDoubleG Posted February 13 Author Share Posted February 13 On 2/6/2024 at 8:12 PM, AustralianPyromaniac said: The only approach for this problem I have come up with would be to mix the barium sulphate in a blender with charcoal in large excess. Then place this mixture in a paint can and heat in a fire for some time, the same way charcoal is made, with vent holes. This should yield the sulphide + CO, which would burn to CO2 in the fire. This should not eat through the metal tin or release toxic fumes. Once this is done, dissolve the resultant mixture in boiling water and filter to remove impurities. The solution which is produced should be of barium sulphide (BaS). This is the answer to the initial question regarding how to get it out of the sulphate form. Although you asked to get it to the carbonate, this is nearly the same. To turn to nitrate, a few approaches can be taken. 1) Mix with balanced amount of ammonium nitrate and bring solution to boil, liberating H2S + NH3 gas by decomp of ammonium sulphide. Solution which remains is barium nitrate and water. The gas released must be scrubbed. (This reaction I am not 100% sure is possible) 2) Mix with magnesium or calcium nitrate to yield a precipitate of poorly soluble Mg/Ca sulphide, and a solution of barium nitrate None of these reactions are ideal. But much simpler than the pathways you proposed. What makes these reactions work is the solubility of the salts involved. You’ll learn in chemistry that the solubility numbers and info given on the internet are often not correct and are misquoted. This can really stuff up calculations. I am currently in Bosnia of all places, and away from all my books and my laptop in Australia, so I have taken values from the internet, but they are often wrong. And some numbers contradict others. Some homework, look up “CRC Handbook of Chemistry and Physics PDF” and download it. Or maybe you can borrow a copy from your local library. You’ll find exact and very reliable values for the solubility of these salts in that book, if you can post them here we’d be able to help you more, and I’d be able to check my work. The ones I am not sure on are the sulphide salts of Mg/Ca/NH4/K/Na. Specifying at STP is enough, but you’ll find solubility across full temp range. None of the above reactions are great pathways and not really what you asked for, as I said earlier, there is no good way to do this. But it should help a bit on what you may want to do. AP. Thanks for the advice, I'll continue to plan this out... and ill also do my homework The second reaction looks like the most doable one to me, I will likely attempt it in the future, if i haven't already made chlorate. And you're right about me posting the solubility, I'll try to post as much information as possible. I somehow didn't think this was super important to the conversation, so I didn't add it in. And sorry for the late response. On 2/9/2024 at 9:46 AM, Powderman said: If source of carbonate would be found this one may help skip the nitric acid: boiling solution of NH4NO3 with BaCO3 works. NH3 and CO2 escape as gas. Yes, but carbonate isn't soluble in water... 2 hours ago, TXpyro said: Just buy some barium nitrate. Can't, sadly. 1 Link to comment Share on other sites More sharing options...
TXpyro Posted February 13 Share Posted February 13 Just now, PillaDoubleG said: Can't, sadly. Oh noooo. Why not? Link to comment Share on other sites More sharing options...
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