Beautiful metal nitrates

[Polverone]

I did a search on this and didn't turn up anything relevant... So I'm going to share how I've been preparing metallic nitrates for pyrotechnics lately.

I've been able to obtain (for free) several pounds of lithium and barium carbonate. These were originally used for ceramics work. Even if you were to buy them they are pretty cheap. Of course they're not much good in pyrotechnics as-is. I looked around for various methods of converting them to nitrates. Most often suggested was "neutralize them with nitric acid." Sorry, don't have that much nitric acid sitting around. One thread on rec.pyrotechnics caught my eye. A guy was boiling together ammonium nitrate and lithium carbonate. The lithium carbonate was eventually converted to nitrate and the ammonium carbonate is unstable when heated, so with 24 hours of boiling he could have a pretty pure lithium nitrate solution. I tried this and it seemed to work okay, but 24 hours at boiling means a lot of babysitting and wasted energy. Plus it wouldn't work with the far less soluble barium carbonate.

Then inspiration struck: convert the carbonates to the soluble chlorides and then add the ammonium nitrate. Dry the whole mess out and heat it hot enough to vaporize/decompose any leftover ammonium nitrate and chloride, since the metallic nitrates are more stable than they are.

I did one batch where I fractionally crystallized my barium chloride to remove traces of calcium contamination (remember, it's ceramics grade) and I just finished another batch where I mixed up the ammonium nitrate, hydrochloric acid, and barium carbonate simultaneously. During the heating stage I ladled damp chunks of my mostly-dried product into a stainless steel dish and heated it with a gas burner until white fumes stopped pouring off and the remaining material melted. The process isn't optimized because the leftover acid attacks the steel, leading to a funky-colored product. You could probably use pyrex instead of stainless steel to avoid this (but then you can't whack the stuff out of the bottom of the container). Or you could use a slight excess of carbonate instead of a slight excess of acid, but I wanted to minimize the number of purification stages I had to deal with. Also, with a larger batch it is hard to heat the whole thing uniformly so that the ammonium compounds go away without decomposing any of the metallic nitrate.

Overall, if you don't want to deal with the expense/fear of buying uncommon (non-fertilizer) nitrates from a lab or pyrotechnics supplier, this seems like a pretty good method. It should generalize to prepare any metal nitrate that has a soluble chloride and a decomposition temperature significantly higher than that of the ammonium compounds. It is worth noting that ceramics suppliers also stock strontium carbonate, in addition to the barium and lithium.

So get yourself a few gallons of HCl and a nice big sack of ammonium nitrate, then start preparing all those lovely, lovely nitrates. I am kind of wondering if I could eliminate the acid also, and just heat a finely ground mixture of barium carbonate and ammonium nitrate, but that is another experiment for another day.

[mongo blongo]

I wouldn't mind having some Barium Nitrate! I read somewhere that you can mix it with H2SO4 and the Barium Sulphate can be filtered out giving very pure HNO3. :)

[Demolition]

And I only find out about this now. :( :p
Does anyone have anymore information about the method mongo mentioned as I have a small amount of barium nitrate.Id be very interested.

[Lagen]

Similar to preparing HNO3 with H2SO4 and Ca(NO3)2. Some definite drawbacks: You will get a porridge-like (with about 30% acids) to almost solid (with conc. ones) ppt of the insoluble sulfate, the HNO3 soaked in it. Almost impossible to fully separate, with a press / centrifuge / frit(expendable)+vacuum you can get a decent yield. With simple filtration (glass filter needed) you will be disappointed. The acid will usually contain a lot of unreacted H2SO4, the nitrate crystals will get covered with the insoluble sulfate and will not react fully. So excess nitrate has to be used, but it's difficult to tell when the H2SO4 is fully eliminated and excess nitrate appears in the mixture... Personally I was very disappointed with this method.

[mongo blongo]

I will try to find it but I can't rember where I saw it! It may take some time.

[vulture]

BaCO3 and SrCO3 can be used as colorizers in pyrotechnic compositions. Keep in mind also that Ba(II) salts are highly poisonous, LD50 inhaled is 500 - 800mg!

Red fire composition #2
Source: "Mengen en Roeren"[6], page 223.
Preparation:
Strontium carbonate...............................16
Potassium chlorate................................72
Powdered shellac..................................12

Red star #3
preparation: Dissolve shellac in boiling ethanol, and add the other ingredients.
Potassium chlorate................................65
Strontium carbonate...............................15
Shellac........................................... 20

For BaCO3 a strong chlorine donor like NH4ClO4 (this is the best oxidizer you can get if you want deep and true colors) is required.
You could also convert it to BaSO4 which is an oxidizer at higher temperatures, this will require a hot primer, for example, KNO3/Al.
Substitution with KClO3 or KClO4 is also possible, then you won't need a chlorine donor anymore.

[mongo blongo]

Couldn't find it but I did find something on it:
Nitric acid
Formula: HNO3

Description: Nitric acid is not used in pyrotechnic compositions but it can be used to prepare a variety of usefull nitrates from carbonates, hydroxides, oxides or free elements. It is used in the explosives industry in the preparation of a lot of commonly used explosives (eg TNT, RDX, PETN, nitrocellulose). Most high explosives have no use in fireworks, though nitrocellulose is used in some fireworks compositions as an acetone soluble binder.

Hazards: Nitric acid is corrosive. The fumes are dangerous to the lungs, eyes and skin. Skin will be stained yellow upon contact. Avoid all contact with both liquid and fumes. Wear eye and skin protection (lab apron, gloves, safety glasses, etc). In some reactions (especially those with metals) a brown gas will develop: nitrogen dioxide. It is very toxic, corrosive and will attack your lungs badly. Only work with nitric acid with adequate ventilation and proper protective clothing. Don't use any solutions more concentrated than 60%. Don't try to prepare high explosives at home and don't allow any organic material to contact nitric acid accidentially because that may result in the formation of dangerously explosive and/or sensitive materials.

Sources: It is possible to prepare nitric acid in several ways. It can also be bought at some drug stores. Here (in the Netherlands) it is sold under it's Latin name, 'acidum nitricum'. Other places where it is sold is at professional gardening suppliers and at welding shops (it is used to passivate stainless steel after welding). One way to prepare it is by distilling a mixture of sulphuric acid and sodium nitrate. This process is dangerous and requires some equipment. This method is probably too dangerous for the average amateur pyro. Another possible method is by precipitating barium sulphate from a barium nitrate solution by adding sulphuric acid. What remains is a nitric acid solution. It should be possible to prepare quite concentrated solutions by using concentrated sulphuric acid and a saturated (-not- hot!) barium nitrate solution. It is important that the sulphuric acid is added to the barium nitrate solution and not the other way around. The mixing of the liquids will produce heat and if the barium nitrate solution is added to the sulphuric acid it could cause sudden boiling and splatting. Therefore, add the sulphuric acid slowly to the barium nitrate while constantly stirring. Allow the mixture to cool from time to time if it gets too hot. A white precipitate of barium sulphate should form. The mixture is then filtered through a sintered glass filter to obtain clear solution of nitric acid.

From <a href="http://www.geocities.com/extremepyro2/cheminfo_EN.html" target="_blank">http://www.geocities.com/extremepyro2/cheminfo_EN.html</a>

[rikkitikkitavi]

I think that heating BaCl2 and NH4NO3 doesent give good yields, because NH4NO3 starts decomposing at the same temperatures where NH4Cl is volatile.
1)
But what if you electrolyse the BaCL2 to BaClO3 ? Then by addition of KNO3 = > preciptate KClO3 :) left is Ba(NO3)2 in solution.
2)
Mix BaCl2 and NaOH => preciptate Ba(OH2) (only partially, it is quite soluble)
Mix Ba(OH)2 and NH4NO3 in solution . boil out the NH3
much quicker beacuse of the the higher OH- concentration , it might work even with solid compounds... (classical laboratory method of
generating NH3, heating Ca(OH2) and NH4CL = NH3 + CaCl2)

/rickard

[kingspaz]

hey, i use a simliar method for preparing calcium nitrate.
i mix CaO (cement) with NH4NO3. then i add a little bit of water and leave it to react. i then filter out excess Ca(OH)2 and CaO and boil away the water from the filtrate. the ammonia will evaporate leaving pure Ca(NO3) :D .....wish i had access to decent chems!

[Polverone]

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> I think that heating BaCl2 and NH4NO3 doesent give good yields, because NH4NO3 starts decomposing at the same temperatures where NH4Cl is volatile. </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Is that in response to my original post? Everything is mixed together in aqueous solution, then evaporated down to chunky residue, then heated at higher temperatures to remove the ammonium compounds. I am *glad* that NH4NO3 and NH4Cl both disappear at relatively low temperatures. I don't want them left in there! I don't know how I would quantitatively assess the products I'm producing but they give vigorous combustion with the appropriate flame colors, so they're pure enough for me. I also don't think I have much leftover BaCl2 after conversion, because the water solubility of my product is pretty poor (as Ba(NO3)2 should be), and this solubility difference also favors formation of the barium nitrate even though HCl and HNO3 are both strong acids (NH4Cl is also less soluble than NH4NO3, again helping things along).

If you would be happier starting with the barium salt of a weaker acid, the acetate and citrate are also soluble. For me, HCl is far cheaper than citric or acetic acid and it seems to get the job done.

[vulture]

I'm looking for an alternative for Ba(II) salts for making green fire since they require preventive measures to avoid severe poisoning.
One of my chemistry books states using borax or boric acid as a green colorizer.
Has anybody tried this?

[Lagen]

It works, but the color is not too intense, because of the low volatility of H3BO3 and B2O3. A much more intense green light can be produced with boric acid ethyl or methyl ester: React EtOH or MeOH with H3BO3 and a small amount of H2SO4 as catalyst, then ignite the mix. To be employed in a pyrotechnic device, the reaction would have to be done just before use, these esters are too volatile to store.

[kingspaz]

what about copper nitrate? wouldn't that give a green flame?

[Lagen]

I haven't had nearly as good results with copper nitrate. Dissolved in alcohol, the flame is <FONT color=9966FF>blue</FONT><FONT color=CC66CC>/</FONT><FONT color=FFCC00>yellow</FONT> as usual, only has a <FONT color=33CC99>green</FONT> border. And a lot of Cu(NO3)2 is needed to produce visible results. I'd guess vulture wanted to use the composition indoors, boron would be better here as it is less toxic. The color produced by copper is a more bluish <FONT color=33CC99>green</FONT>, while boron produces a grass <FONT color=80FF40>green</FONT> color. Barium however gives a <FONT color=CCFF66>green</FONT> color.

Only very little H3BO3 and a few drops 96% H2SO4 dissolved in alcohol produce a <FONT color=80FF40>completely green flame</FONT> in an alcohol lamp! (The flame must not be too big otherwise it has a <FONT color=FFFF00>yellow</FONT> cone inside.) Very nice for effect. Another really beautiful color is <FONT color=FF3399>lithium nitrate</FONT> in alcohol.<FONT color=003366>

<small>[ March 30, 2002, 09:23 PM: Message edited by: Lagen ]</small>

[Polverone]

I will have to try those boric acid esters. I've made esters out of just about every other acid just from curiosity. It would be nice to have an application for once.

Lithium nitrate may give very beautiful flames with alcohol, but lithium chloride does too and it is easier to make than lithium nitrate. Both the nitrate and the chloride are annoyingly deliquescent. If you ever want to make pyro comps with them you'll have to mix everything up just minutes before firing, unless you live in a desert.

Unless you are planning on inhaling the smoke from your pyro comps, I don't think you need to worry too much about the barium toxicity. Wear a dust mask and gloves, clean up before eating, and you should be fine (unless you are really sloppy). But the best greens are supposed to be made with barium chlorate, not nitrate, and I don't have an easy way in mind to that. Perhaps you could electrolyze hot BaCl2 solution as when making NaClO3. That's too much trouble for me, at the moment.

[Lagen]

Sure, any lithium compound that dissolves in the fuel will do. :o <img border="0" title="" alt="[Wink]" src="wink.gif" /> I just have plenty of the LiNO3 around, it's good as a catalyst for RDX synthesis.

[vulture]

Well, i wasn't thinking of using it indoors, i was more worried about the preparation in which i would expose myself to toxic barium salts. It was to be used in fountains and outside. Just because i get bored about the white Al fountains i make.

I'm also thinking about Zn/S or Zn/KClO3 as a colorizer.

Now before anyone get's a wrong impression, borax and boric acid are toxic too, LD50 is 5g, but the LD50 of Ba(NO3)2 is 500-800mg, see what i mean?

[Lagen]

I think the lethal dose of H3BO3 is about 5g, but for borax it's 5g/kg, or several hundred grams per human. Therefore borax is much less toxic.

The toxicity of the barium compounds (chloride is about the same) is striking, it's up there with cyanides! It's interesting however, that the bottles in which I'm getting BaCl2 have just a "harmful" symbol on the label! And early in the commie times there were sparklers contg. a lot of Ba(NO3)2 (I believe some are still available), there was a lot of poisonings...

[vulture]

The 2001-2002 catalogue of my chem supplier also states harmful and the sparklers that i use contain it to, i hold them with bare hands...

Which one gives a nicer color, boric acid or borax?

<small>[ April 02, 2002, 10:10 AM: Message edited by: vulture ]</small>

[Polverone]

See <a href="http://digitalfire.com/education/toxicity/barium_english.shtml" target="_blank">http://digitalfire.com/education/toxicity/barium_english.shtml</a>
It gives a lower-end human lethal dose of barium salts at around 1 g.
<a href="http://www.emedicine.com/med/topic487.htm" target="_blank">http://www.emedicine.com/med/topic487.htm</a> gives a lower-end lethal human dose of cyanide salts at around 200 mg. So the barium and cyanide are within an order of magnitude of each other. Hmm, how lethal would barium cyanide be?

There are some significant differences still between (say) NaCN and BaCl2. The NaCN is very fast acting as a poison. On the other hand, barium will accumulate to a greater extent than cyanides. So which is more dangerous depends on the conditions of exposure. BaCl2 is much safer in the sense that it does not release lethal gas on contact with acids. I still stand by my statement that barium compounds can be safely manipulated with common-sense precautions. As for cyanides, I think people tend to overestimate the lethality since they are the stereotypical poison of murder mysteries.

[Lagen]

vulture: Regarding borax (the decahydrate...) - There's not a great choice of solvents to try this with, I tried a mixture of boiling alcohol with conc. glycerol with some borax dissolved in it. Lighting it, it's the same story as with copper nitrate, some green color appears, but only on the outside of the flame. (The green is similar to that produced with boric acid.) The yellow color of sodium is dominant. Of course, anhydrous sodium tetraborate is a little soluble in methanol, but I don't see a point in trying it. It's not of much use if a pure green color is desired.

Regarding the classification of barium compounds as poison - I checked Aldrich, they state both "toxic" and "harmful" hazard phrases for most barium compounds. I can really think of just one reason why BaCl2 tends to be "non-toxic" sometimes... Maybe it's so important for laboratory work, that putting it on the toxic chemicals list would deny access to it for too many small business/industrial labs which use it for analytic/supportive purposes only, and are not licensed for handling toxic chemicals. The licensing and record keeping requirements are a fuss, I know it's been common practice in Western countries but over here lab people just learn to live with them. They rather go with "you scratch my back" deals with the supplier. Same as with gasoline, it's just a matter of money and lobbystic pressures. Everyone can buy an unlimited amount of it at the gas station, supermarket etc., but if you want to purchase a liter for your lab, you're told it's toxic, carcinogenic and requires a license (a guy with a university degree in chemistry, several years of practice, approval...), record keeping and reporting etc. Some suppliers will just cover their ass and of course some will try to mark it as "Cleaning Fluid. Harmful"...

Polverone: I didn't want to say barium was exactly as toxic as cyanides. I judged by the figures stated in the Merck Index - KCN - 10mg/kg, NaCN - 15mg/kg, Ba - 19-20 mg/kg (30 mg/kg BaCl2). (Sure HCN itself is more toxic than cyanides and an approximate LD for the whole body is 50-60 mg.)

[vulture]

So i could manipulate bariumnitrate safely when wearing gloves, dust mask and goggles? At rec.pyrotechnics they advise drinking epsom salt (MgSO4) solution while working with it, as this converts it to BaSO4 which is relatively harmless because it's insoluble.

[Polverone]

I'm sure the magnesium sulfate would do a good job of rendering any ingested barium salts harmless. I don't think it's necessary unless you have reason to believe that you've recently ingested some - though it won't hurt in any case. Gloves, goggles, and a dust mask should afford perfectly adequate protection. There are many things more worrisome than barium nitrate in my lab, and I've yet to suffer any sort of injury. Basically, keep your workspace neat and clean and use protection, and you'll be fine.

[Boob Raider]

Unrequired amounts of MgSO4.6H2O will make you shit a lot :D (thats the only harm I can think of). So drink up if you have even the slightest amount of doubt, that you might have gotten some Ba2+ in you (Its better to shit than to get poisoned) :p . BaSO4 is one of the most insoluble substances known. Are there any cheap and easy sources for Zirconium and Titanium, and do their salts color flames or is it only the burning metal.

[Guerilla]

well.. when I made my first batch of Ba(NO3)2, from carbonate and AN.. I didn´t wear any goggles, gloves or such and I handled it almost like any other nitrates with no special precautions.. That was very stupid, after a while I was feeling sleepy and got a nice head aches. So, at least gloves are essential when messing with this stuff.

Anyways. Bariumnitrate brightens a flame nicely, but a chlorine donor is of course essential if good green is wanted.. This might be a bit off topic but, what are you guys using as the colour enhancer? Parlon would be ok, but I don´t know where should I ask it from, also getting good solvent for PVC and Saran(cling wrap) has been a problem so far. I read from the rec.pyrotechnics FAQ that both pvc and saran are soluble in tetrahydrofuran(THF). Does any of you know what´s the origin use for this THF and is it possible to get from a local hardware store? :confused:

<small>[ November 07, 2002, 06:47 AM: Message edited by: Guerilla ]</small>

[nbk2000]

PVC pipe glue contains PVC dissolved in THF, so you'd be set right there. :)

[blindreeper]

If I ring up a ceramic supplier and ask for these various carbonates and they ask me what they are used for what do I tell them? Basicly what are they used for in ceramics?

[Boob Raider]

Yeah ... I was kinda wondering about the same thing. I ask the dealer to give me Cr2O3 or "Chrome Green" or something like that. Do compounds need to be reffered to by their trade names or chem names are fine.

[VX]

When I went, I asked for the Chem name, because it was more apropriate because of the reason I was going to give for wanting them. Which was that I am a chemistry student, and was using them in an experiment. In a way, its true :D . The three people I spoke too all new the pigments by their chem names. Specificaly, Iron oxide, strontium carbonate and copper oxide (He even asked me which copper oxide I wanted)

However my problem came when the manager refused to sell me anything less than a 100kg drum of each :rolleyes: . I never got around to trying somewhere else, although I will be doing soon

[Boob Raider]

I don't know about that here. I don't want to take a chance .... some people are real Assholes like one dude at the hydroponics store. I ask him the price for a 2.5 kg bucket of KNO3 and he looks at me weird and says "Ahh nobody buys this stuff" (well dumb ass I want to and why the fuck are you selling it then :mad: ). So I want to totally avoid this situation. I don't even know what TNT stands for when it comes to buying stuff also meant for other use (meaning I don't even have grade 10 chemistry knowledge and I will only use products for what they are labled for and not as a source of chemicals). All that these dumb ass can do is "humm .... a 23-25 yr old dude with chemistry knowledge who is buying chemicals is probably going to a) Start up a drug lab. 2) Blow something up. 3) Do both :mad: . So if someone knows the trade names and /or a site with trade names corrosponding to the chem names .... would be greatly appreciated. :)

[Sparky]

I'll share my experience on chemical aquiring:
If you go and say you want to make pottery stuff, they will likely ask you what you want it for. So, you have to know. Unless you say you are buying it for someone else. Such as "I'm getting it for my dad's birthday. These weird chemicals were on his list, I don't know what the're used for." Christmas is coming you know <img border="0" title="" alt="[Wink]" src="wink.gif" /> . Then you don't have to know anything about the chemicals use in pottery.

Instead of going into the hardware store and asking for "stump remover" right off, beat around the bush. Obviously this is over the phone as if you were in the store you would just go to the lawn care section and look. Tell them you have this big stump in your lawn you dad wants you to take out. Do they have anything for that? If they don't mention potassium nitrate give them a subtle push like "What about that stuff that makes it rot really fast? Someone recommended it." Using a brand name is good. Make them suggest that you should buy potassium nitrate.

If at all possible bring someone old. I get a lot more respect when my dad comes. If they think something's up they will probably just say they don't have the product. Once I went into a hydroponics store with my friends (stupid move) and straight out asked for potassium nitrate (stupid move). They said they didn't have any. Ya right :rolleyes: .

[Helos]

Vulture: find it very strange that you say bariumnitrate has a LD 50% of 500-800mg. In my container it is only marked as harmful. Also LD stands for "liquid dose" right ? (and not for lethal dose like you may first think) And you suggest that it has a LD50% when it is inhaled!? I think it is GD 50% then...

[VX]

LD50 means lethal dose, from here <a href="http://www.ccohs.ca/oshanswers/chemicals/ld50.html" target="_blank">here</a>

Barium Nitrate is hightly toxic, as are all soluble barium compounds. Acording to <a href="http://physchem.ox.ac.uk/MSDS/BA/barium_nitrate.html" target="_blank">this site</a> , it has an LD50 of just 355 mg kg-1 in rats.

[vulture]

Helos I did not say Ba compounds had a lethal inhaled dose of 500-800mg, that is the LD50.
I just said the dust could be breathed and then it's toxic too, so you better wear a mask or something.

Please read somewhat more carefully.

<small>[ November 14, 2002, 04:54 PM: Message edited by: vulture ]</small>

[Anthony]

Helos, also note that it's 355mg per kilo of body mass. Your average guy weighs about 70kg+ so you'd have to eat 25gm of it to reach LD50.

[Helos]

Ok, i understand!
I am sorry about thinkin LD 50 was liquid dose, I had get that wrong.
Then BaNo3 are not that extremly toxic, like methanole or TNP, but more intresting is what long-time effects it give.
I am not afraid for dying inhaling metals dust or mercury but I dont want to do it beacause of that reason.

[Boob Raider]

Heleos .... you should be afraid of the consequenses of inhaling stuff like that ..... only then would you be careful in handling them. You have to respect the chemicals for their ability to harm us in so many ways. Respect them and they are predictable ... don't, and they WILL fuck you over ... real good.
Take care.

[knowledgehungry]

In reply to the much earlier post about using Ba(NO₃)₂ to produce HNO₃ i had an experience with the salt soaking up the acid. It was a gooey mess of Nitric and sulfate. I used Silver nitrate for the attempted synthesis(don't worry i didnt pay for it) and could not separate the results.

[mr.evil]

maybe not very usefull, but i've made Strontiumchloride, by neutralising HCl with SrCO3.

when i hold 1 crystal in a gas flame, the flame becomes bright red... But there are some HCl traces left in it, so coughed as an imbecil...

[blindreeper]

With your strontium chloride, you could electrolize it to make Sr(ClO3)2 then use that to make Sr(ClO4)2 via electolisis. Just a though or am I talking through my ass again?

-----------------------------------------------

YES you are! you talk as though electrolising to the chlorate is different to using electrolyisis to make the perchlorate. they are the same god dam thing. don't post stuff you are not sure about!! it can cost lives in this hobby.-kingspaz

<small>[ December 03, 2002, 05:36 PM: Message edited by: kingspaz ]</small>

[Marvin]

Electrolysis of group 2 metal chlorides to make chlorate usually isnt an option anyway, oweing to the low solubility of the hydroxide and its effect on the resistivity of the cell.