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woelen
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Heavy metal chlorites
Last weekend I investigated the properties of lead chlorite. This chemical is easy to make by precipitation. Simply mix a solution of NaClO2 and a
solution of Pb(NO3)2. Both solutions should not be too strongly concentrated.
When this is done, a yellow precipitate is formed, which has a color, very much resembling the color of powdered sulphur. This precipitate can be
washed with distilled water and then can be dried.
It has energetic properties. When a small amount of the dry powder is heated in a test tube, then it explodes with a loud POP noise and white smoke is
produced. When it is kept in an open flame, it very quickly burns (like good quality black powder) with a pale flame, producing white smoke. The funny
thing is that this material does not require any fuel for quick burning or explosion. This is in strong contrast with NaClO2 which only burns with
fuels like sugar, sulphur or red phosphorus.
I do not know about its long term stability. I keep appr. 500 mg of this material in a small vial and after one day of storage no deterioration can be
observed.
Have any of you experience with other heavy metal chlorites? Next one I want to try is the silver salt.
Please, if you do experiments with this, be careful. Chlorites are very reactive and at low pH you get the explosive gas ClO2. Besides that, lead
is toxic and the white smoke from burning/decomposing Pb(ClO2)2 certainly should not be inhaled!
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DraconicAcid
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I'm impressed by your courage in working with this material.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Bert
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New material to me-
Perhaps you could try hitting a small pinch with a hammer on a steel anvil, or place a few mg on a porcelain tile and rub hard with a similarly hard
tool- Just a quick and rough check for impact and friction sensitivity. If you use a mortar and pestle, be aware that hot Lead oxide tends to melt
itself into glassy substances, so don't use your favorite tools.
The reaction products from that burning, Lead oxide(s)? Lead chloride???
And from this earlier thread:
http://www.sciencemadness.org/talk/viewthread.php?tid=3314
Per Axt i this thread, PATR says the mixture of Lead chlorite and sugar is explosive, to the degree it may be used as a primary?!
Lots of old references to Lead chlorite either spontaneously burning on contact with Sulfur, or firing on slight friction.
Further descriptions of Silver and Mercury chlorites as being explosive- Not going to try Mercury, myself.
[Edited on 29-11-2016 by Bert]
Rapopart’s Rules for critical commentary:
1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it
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2. List any points of agreement (especially if they are not matters of general or widespread agreement).
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Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).
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woelen
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I am willing to try the silver salt and maybe copper and other row one transition metals. I do not try the mercury salt. Producing smoke of a mercury
salt is not good at all. Mercury is much more toxic than lead and even lead is borderline already for me (hence I only tried ultra small amounts of 10
mg or so in open air and tried a little bit more like 50 mg in a test tube).
The chlorites are interesting, however, to experiment with and if you use very small quantities (appr. 50 mg) in the experiments, then the risk in
terms of explosion or fire at least are acceptable. With such small quantities you do not run the risk of blowing up your hand or getting big things
on fire.
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PHILOU Zrealone
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@Woelen,
I know from a long time that Pb, Ag and Hg chlorite are interesting alone for energetic material (research), but I have never had easy acces to pure
chlorite so I never made those.
Thanks to you now I know for sure what is written in old books is right ![:)](./images/smilies/smile.gif) ![;)](./images/smilies/wink.gif) ![:P](./images/smilies/tongue.gif) .
Now one step further:
-Test mixes (carefully since probably more sensitive than chlorate)
-Test complexes (ethylene diamine, ...) ammonia will probably be too dangerous
--> Axt already tested AgClO2 and N2H4...decomposed into fumes upon contact.
[Edited on 30-11-2016 by PHILOU Zrealone]
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Tdep
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I think this thread is convincing me to buy some sodium chlorite, but when you say 'pure chlorite', it only ever comes as an 80% grade yeah? There's a
source roughly nearby me on eBay for $21/200g including shipping and I think that's an alright-ish price
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woelen
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It can be made at higher purity, but this is not stable. If you have pure NaClO2, then it decomposes to NaCl, NaClO3 and possibly some O2 as well.
With increasing concentration of NaCl the decomposition slows down until at appr. 20% concentration of NaCl the decomposition comes to a halt
completely. In the commercial product NaCl is added intentionally to prevent further decomposition and formation of NaClO3, especially when the
material is used for human consumption (e.g. in decontamination of water, or when used as MMS). Hence, the product you can buy has 20% NaCl and 80%
NaClO2. The 20% NaCl is no issue though in most experiments.
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PHILOU Zrealone
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | It can be made at higher purity, but this is not stable. If you have pure NaClO2, then it decomposes to NaCl, NaClO3 and possibly some O2 as well.
With increasing concentration of NaCl the decomposition slows down until at appr. 20% concentration of NaCl the decomposition comes to a halt
completely. In the commercial product NaCl is added intentionally to prevent further decomposition and formation of NaClO3, especially when the
material is used for human consumption (e.g. in decontamination of water, or when used as MMS). Hence, the product you can buy has 20% NaCl and 80%
NaClO2. The 20% NaCl is no issue though in most experiments. |
No issue, except the fact that chlorides of the heavy metals of interest are also precipitated... ![:(](./images/smilies/sad.gif)
--> Hg2Cl2 (but not HgCl2 what is soluble to some extend)
--> PbCl2
--> AgCl
So if you used that brand of NaClO2/NaCl (80/20) the Pb(ClO2)2 you made also contains PbCl2...![:(](./images/smilies/sad.gif)
and knowing that the solubility increases from PbCl2 to Pb(ClO4)2, one may conclude that PbCl2 < Pb(OCl)2 < Pb(OClO)2 < Pb(OClO2)2 <
Pb(OClO3)2 ("<" = less soluble than)...
so the energetic properties of the Pb(ClO2) are far from what it should be ( ![:D](./images/smilies/biggrin.gif) ![:)](./images/smilies/smile.gif) ![;)](./images/smilies/wink.gif) ) because most of the precipitate is tempered by a vast amount of PbCl2 (probably
larger than 20%) .
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Tdep
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Interesting about the decomposition, how does the NaCl stabilize the chlorite like that? It all happens in the solid state, I wouldn't have thought
such a thing happened.
Ok so to see the best the heavy metal chlorites can do, the chloride must really be removed. How are we going to do that? I suppose you could
fractionally crystallise it out, given that the chlorite has over three times the solubility?
Actually no, a better option might be to first add a ~0.3Mol equivalent of Ag(NO3) to the technical grade sodium chlorite, give it a bit of
time to equilibriate and then filter. That should remove the chloride and leave just the chlorite, or at least heavily enrich the chlorite/chloride
ratio?
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PHILOU Zrealone
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Quote: Originally posted by Tdep ![](images/xpblue/lastpost.gif) | Interesting about the decomposition, how does the NaCl stabilize the chlorite like that? It all happens in the solid state, I wouldn't have thought
such a thing happened.
Ok so to see the best the heavy metal chlorites can do, the chloride must really be removed. How are we going to do that? I suppose you could
fractionally crystallise it out, given that the chlorite has over three times the solubility?
Actually no, a better option might be to first add a ~0.3Mol equivalent of Ag(NO3) to the technical grade sodium chlorite, give it a bit of
time to equilibriate and then filter. That should remove the chloride and leave just the chlorite, or at least heavily enrich the chlorite/chloride
ratio? |
Following what Woelen wrote,
One may assume that there is an equilibrium disproportionation reaction at work (into the dissolved state).
3NaOClO <===> NaCl + 2NaOClO2
or
2NaOClO <===> NaCl + NaOClO2 + 1/2 O2
Fractional crystallisation yes like you wrote.
or
Fractional dissolution/solvatation (but one needs to know better the properties of halides vs chlorites into specific solvents and relation to
temperature).
or
Fractional precipitation like you wrote.
Assuming no chlorate formation during purification proces...purity may be assessed by O2 content (probably by heating moderately with a minute MnO2
amount (like it is done for chlorates)).
[Edited on 4-12-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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woelen
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I did my experiments with Pb(ClO2)2 with the 80% NaClO2 which can be obtained from eBay. I have no access to 100% pure NaClO2 and that would not
remain pure anyway.
The 80% material works fine and the Pb(ClO2)2 obtained with this is highly energetic.
The simple order, given by PHILOU Zrealone, does not hold.
Pb(ClO)2 does not exist, it immediately has an internal oxidation reaction in which the lead(II) is oxidized to lead(IV). If you add some hypochlorite
to a solution of a lead(II) salt, then you get a brown precipitate of PbO2.
Pb(ClO2)2 probably is less soluble than PbCl2, otherwise indeed I would have obtained a lot of PbCl2 with just a little Pb(ClO2)2 in it. I do not
think that my Pb(ClO2)2 is 100% pure, but I am quite sure that it is does not contain more than 20% PbCl2.
I think that the order of solubility for the lead salt is something like Pb(ClO2)2 < PbCl2 << Pb(ClO3)2 ~ Pb(ClO4)2.
For the silver salt, things may indeed be somewhat more problematic. AgCl is really insoluble, while PbCl2 is somewhat soluble. For the copper salt,
CuCl2 is soluble, so with that there is no issue.
This week I hope to find some time for the experiments suggested by PHILOU Zrealone. I do have ethylene diamine and I can try with hydrazine hydrate.
With the latter I expect immediate decomposition though. If you add solid NaClO2 to hydrazine hydrate then you get an immediate violent reaction (I
once tried that) and I do not expect otherwise with lead chlorite.
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PHILOU Zrealone
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | I did my experiments with Pb(ClO2)2 with the 80% NaClO2 which can be obtained from eBay. I have no access to 100% pure NaClO2 and that would not
remain pure anyway.
The 80% material works fine and the Pb(ClO2)2 obtained with this is highly energetic.
The simple order, given by PHILOU Zrealone, does not hold.
Pb(ClO)2 does not exist, it immediately has an internal oxidation reaction in which the lead(II) is oxidized to lead(IV). If you add some hypochlorite
to a solution of a lead(II) salt, then you get a brown precipitate of PbO2.
Pb(ClO2)2 probably is less soluble than PbCl2, otherwise indeed I would have obtained a lot of PbCl2 with just a little Pb(ClO2)2 in it. I do not
think that my Pb(ClO2)2 is 100% pure, but I am quite sure that it is does not contain more than 20% PbCl2.
I think that the order of solubility for the lead salt is something like Pb(ClO2)2 < PbCl2 << Pb(ClO3)2 ~ Pb(ClO4)2.
For the silver salt, things may indeed be somewhat more problematic. AgCl is really insoluble, while PbCl2 is somewhat soluble. For the copper salt,
CuCl2 is soluble, so with that there is no issue.
This week I hope to find some time for the experiments suggested by PHILOU Zrealone. I do have ethylene diamine and I can try with hydrazine hydrate.
With the latter I expect immediate decomposition though. If you add solid NaClO2 to hydrazine hydrate then you get an immediate violent reaction (I
once tried that) and I do not expect otherwise with lead chlorite. |
Thank you for the clarification.
I just want to say that PbO2 may result from Pb(2+) with ClO(-) because commercial hypochlorite contains a lot of OH(-).
--> Oxydo redox potential generally express into acidic or into basic media...but does this reaction stil happens when in neutral aqueous media?
About hydrazine chlorite...I have never found infos about it but wel over hydrazine chlorate, perchlorate and diperchlorate.
Axt did test AgClO2 with hydrazine, but then the decomposition must be due to the Ag(+) with what hydrazine is uncompatible (see AgNO2 and AgNO3
decompose into a silver mirror...although in books the nitrate is supposed to deliver AgN3)...with Pb(ClO2)2 it is terra incognita.
--> Be very cautious --> soft plastic beaker and minute amount
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woelen
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Right now, I have the Pb(ClO2)2 standing for two weeks and it still is as good as when I made it. This stuff appears to be stable on storage. Quite a
few chlorites are said to be unstable, but the lead-salt is not.
It is unstable in contact with hydrazine. Making a complex with hydrazine is not possible. It reacts immediately with hydrazine. I think that this is
due to incompatibility of chlorite with hydrazine, regardless of the cation in the compound.
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | Right now, I have the Pb(ClO2)2 standing for two weeks and it still is as good as when I made it. This stuff appears to be stable on storage. Quite a
few chlorites are said to be unstable, but the lead-salt is not.
It is unstable in contact with hydrazine. Making a complex with hydrazine is not possible. It reacts immediately with hydrazine. I think that this is
due to incompatibility of chlorite with hydrazine, regardless of the cation in the compound. |
It seems right conclusion...Pb(2+) is unreactive towards hydrazine...so the chlorite must be responsible. How did the reaction proceed? Massive gas
evolution, puff, flame?
Where both compounds into solution (cooled or not) or the solid Pb(ClO2)2 into the liquid hydrazine (concentrated or not)?
Maybe a hydrazine complex may form with another cation...Hg do form nice complexes with amines...Zn, Co, Fe, Cd, Ca, Mg remains to test and Cu which
will most likely be very unstable.
1°)I did made some truquoise blue Cu(N2H4)2(NO3)2 complex from conc Cu(NO3)2, ethanol and N2H4.H2O (80% hydrazine) while most did turn into N2, Cu
and Cu2O brown sponge; the remaining turquoise blue complex precipitate decomposed in big part by itself when drying (self inflamation) and a tiny
part remained as very inflamable and energetic compound (burning with a nice blue-green flame).
2°)I did put NaNO2 cristals into hydrazine hydrate (N2H4.H2O / 80%N2H4) with phenol phtaleine solution. The red-violet colour dissapeared without gas
bubbles nor heating while the NaNO2 cristals dissolved...so something happened.
I was hoping that since into books AgNO2 (or AgNO3) turns into AgN3 upon exposure to N2H4; maybe some NaN3 would form...but the study was not pursued
further.
To confirm unstability of hydrazine with chlorites, could you just mix a little of your NaClO2/NaCl with hydrazine?
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woelen
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The reaction with the hydrazine is not really violent, it just is fast. The yellow solid, when added to a solution, containing 30% or so of hydrzine,
turns white at once and falls apart and makes a cloudy white liquid.
I also did other experiments with the Pb(ClO2)2:
- Grind it with a metal spatula while pressing it hard and putting strong force on it. This does not ignite the material. The final result is a yellow
powder, looking like sulphur.
- Mix the yellow powder with sulphur (appr. same volume of powdered sulphur mixed carefully with the lead chlorite). When this mix is ignited it burns
very fast with a peculiar grey/blue flame color. The burning is not explosive though. Ignition is remarkably easy. You do not have to keep it in a
flame, just keeping the mix near a flame is enough to ignite it.
- Mix the yellow powder very carefully with red phosphorus. Tap the mix with a glass rod. This leads to a small explosion. The mix gives a high
pitched report (PANG) and produces a wonderful smoke ring which rises up slowly and becomes wider while rising up.
- Mix the yellow solid with a solution of ethylene diamine in water. The material slowly turns white. It does not dissolve, the liquid becomes cloudy.
I think that no complex is formed, the material simply hydrolyses, forming Pb(OH)2, free ClO2(-) ions and protonation of some of the ethylene diamine.
Nothing interesting.
I will try adding NaClO2 to a solution of hydrazine. In the past I have done the experiment of adding NaClO2 to a solution of N2H4.2HCl. That leads to
a very violent and dangerous reaction. Using plain hydrazine and not the hydrazinium salt may lead to different results, however. It will come back on
that.
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Maybe you could add a couple of milliliters of an organic slightly polar solvent (ethyl-acetate e.g.), to the reaction mixture of the ClO2-
with the ethelyne diamine. If you are partly oxidizing the amine groups the white stuff should dissolve in the organic layer, if it is
Pb(OH)2 it should not.
It would be interesting to see such a aquous oxidation of an organic compound.
Edit: If it is an oxidation it should also give an white percipitate with NaClO2
[Edited on 13-12-2016 by Tsjerk]
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Quote: Originally posted by Tsjerk ![](images/xpblue/lastpost.gif) | Maybe you could add a couple of milliliters of an organic slightly polar solvent (ethyl-acetate e.g.), to the reaction mixture of the ClO2-
with the ethelyne diamine. If you are partly oxidizing the amine groups the white stuff should dissolve in the organic layer, if it is
Pb(OH)2 it should not.
It would be interesting to see such a aquous oxidation of an organic compound.
Edit: If it is an oxidation it should also give an white percipitate with NaClO2
[Edited on 13-12-2016 by Tsjerk] |
The oxydation of the amines may lead to:
-N-hydroxylamine (R-NHOH about as oxydable as hydrazine)
-chloramine (R-NHCl)
-nitroso compound or resonance form aldehyde oxime (R-CH2-N=O <==> R-CH=N-OH)(*)
-dichloramine (R-NCl2)
-nitro group (R-NO2)
-cyano group (R-C#N)
And further oxydation products by O or Cl.
(*) Note that nitrosocompound can be seen as a dehydrated from of a putative N,N-dihydroxylamine
R-CH2-N(OH)2 <==> R-CH2-N=O + H2O
[Edited on 13-12-2016 by PHILOU Zrealone]
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | The reaction with the hydrazine is not really violent, it just is fast. The yellow solid, when added to a solution, containing 30% or so of hydrzine,
turns white at once and falls apart and makes a cloudy white liquid.
I also did other experiments with the Pb(ClO2)2:
- Grind it with a metal spatula while pressing it hard and putting strong force on it. This does not ignite the material. The final result is a yellow
powder, looking like sulphur.
- Mix the yellow powder with sulphur (appr. same volume of powdered sulphur mixed carefully with the lead chlorite). When this mix is ignited it burns
very fast with a peculiar grey/blue flame color. The burning is not explosive though. Ignition is remarkably easy. You do not have to keep it in a
flame, just keeping the mix near a flame is enough to ignite it.
- Mix the yellow powder very carefully with red phosphorus. Tap the mix with a glass rod. This leads to a small explosion. The mix gives a high
pitched report (PANG) and produces a wonderful smoke ring which rises up slowly and becomes wider while rising up.
- Mix the yellow solid with a solution of ethylene diamine in water. The material slowly turns white. It does not dissolve, the liquid becomes cloudy.
I think that no complex is formed, the material simply hydrolyses, forming Pb(OH)2, free ClO2(-) ions and protonation of some of the ethylene diamine.
Nothing interesting.
I will try adding NaClO2 to a solution of hydrazine. In the past I have done the experiment of adding NaClO2 to a solution of N2H4.2HCl. That leads to
a very violent and dangerous reaction. Using plain hydrazine and not the hydrazinium salt may lead to different results, however. It will come back on
that. |
Thank you for those valuable experiments and reports.
About cloudy EDA and "nothing interesting", I think that it is actually a very interesting fact...maybe a way to safely make (a probably unmade to
date) EDA dichlorite!
[Edited on 13-12-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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woelen
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EDA dichlorite would be very interesting. How would you make this compound? Adding a chlorite salt to a solution of EDA does not work. EDA is quite
basic and chlorite is the conjugate of a fairly weak acid (HClO2). One should be able to isolate HClO2 (dissolved in water) and mix this with a
solution of EDA.
One possible route to EDA dichlorite could be making EDA perchlorate (which is not difficult, I have done this myself from EDA and perchloric acid)
and mixing a solution of that with a solution of potassium chlorite. KClO4 will precipitate, the protonated EDA ions and the chlorite ions remain
behind in solution.
Unfortunately I know of no source for KClO2. On eBay I only see sellers of NaClO2 and this trick does not work for sodium salts, due to the high
solubility of NaClO4. Making KClO2 yourself in a safe way is not going to be easy. One possible route is to bubble ClO2 through a solution of KOH to
which H2O2 is added as well, but this reaction is quite dangerous, due to the explosive nature of ClO2.
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DraconicAcid
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | EDA dichlorite would be very interesting. How would you make this compound? Adding a chlorite salt to a solution of EDA does not work.
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It was just suggested that Pb(ClO2)2 + EDA + 2 H2O -> Pb(OH)2(s) + H2EDA(ClO2)2(aq) might work.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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PHILOU Zrealone
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Quote: Originally posted by DraconicAcid ![](images/xpblue/lastpost.gif) | Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | EDA dichlorite would be very interesting. How would you make this compound? Adding a chlorite salt to a solution of EDA does not work.
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It was just suggested that Pb(ClO2)2 + EDA + 2 H2O -> Pb(OH)2(s) + H2EDA(ClO2)2(aq) might work. |
Yes DraconicAcid you got it ![;)](./images/smilies/wink.gif)
Woelen didn't realise that what he wrote was actually the solution..."the material simply hydrolyses, forming Pb(OH)2, free ClO2(-) ions and
protonation of some of the ethylene diamine." ![:D](./images/smilies/biggrin.gif)
If Pb(OH)2 precipitates and doesn't complexate then only H(+), EDA and ClO2(-) remains into solution --> filtration and cristallization --> EDA
dichlorite.
Although his new proposal of KClO4 precipitation is also a valid one.
ClO2 can be made safely from oxalic acid and NaClO3 but it is then dilluted with CO2 what may be anoying to get pure KClO2 since KHCO3 and K2CO3 will
enter into account.
[Edited on 13-12-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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woelen
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Yeah, you're right. I must have been sleeping while writing the previous post ![;)](./images/smilies/wink.gif)
I will do this experiment with a small amount of Pb(ClO2)2. In a practical experiment I think that you should add a slight excess of EDA to be sure
that all chlorite is used and allow the water and excess EDA to evaporate while drying the material.
I am afraid that solid H2EDA(ClO2)2 (if it exists and does not decompose already before it becomes really dry) is a very sensitive chemical. In my
experience, chlorite, combined with fuel, is more sensitive/reactive than chlorate, combined with the same fuel. And you all know how sensitive
chlorate based mixes are, so what would be the chlorite based mix?
But nevertheless, it is worth a try. I have appr. 300 mg of my Pb(ClO2)2 left and I will use it up in the EDA experiment.
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If you use excess EDA, then surely you will get HEDAClO2.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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woelen
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I added some EDA to the remaining amount of my Pb(ClO2)2. I first added the solid to some water and I had to add 3 big drops of EDA to have all of it
converted to a white solid. Two drops was not enough, three drops was an excess amount. So, there is some excess amount.
Now I have a cloudy white liquid and I allow the white solid to settle at the bottom. Tomorrow I will pipette away the clear liquid and allow this to
evaporate. I hope that solid material remains behind. This may become HEDA(ClO2), or a mix of H2EDA(ClO2)2 and HEDA(ClO2). Both are interesting. First
let's see whetther it is possible at all to get an interesting energetic compound. Further optimizations always can be done in the future with a new
batch of Pb(ClO2)2.
--------------------------------
As another experiment, I added solid NaClO2 to 30% N2H4 in water. This does not react, not even after 15 minutes of waiting. Next, I added a small
amount of dilute H2SO4. When this is done, then after a short delay, suddenly a violent reaction starts in which a colorless gas is formed (most
likely N2) and after a while the liquid suddenly turns yellow (formation of ClO2). So, first, when there still is N2H4, the chlorite is reduced to
colorless chloride, but once the hydrazine is used up, the remaining chlorite reacts with formation of ClO2.
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Quote: Originally posted by woelen ![](images/xpblue/lastpost.gif) | I added some EDA to the remaining amount of my Pb(ClO2)2. I first added the solid to some water and I had to add 3 big drops of EDA to have all of it
converted to a white solid. Two drops was not enough, three drops was an excess amount. So, there is some excess amount.
Now I have a cloudy white liquid and I allow the white solid to settle at the bottom. Tomorrow I will pipette away the clear liquid and allow this to
evaporate. I hope that solid material remains behind. This may become HEDA(ClO2), or a mix of H2EDA(ClO2)2 and HEDA(ClO2). Both are interesting. First
let's see whetther it is possible at all to get an interesting energetic compound. Further optimizations always can be done in the future with a new
batch of Pb(ClO2)2.
--------------------------------
As another experiment, I added solid NaClO2 to 30% N2H4 in water. This does not react, not even after 15 minutes of waiting. Next, I added a small
amount of dilute H2SO4. When this is done, then after a short delay, suddenly a violent reaction starts in which a colorless gas is formed (most
likely N2) and after a while the liquid suddenly turns yellow (formation of ClO2). So, first, when there still is N2H4, the chlorite is reduced to
colorless chloride, but once the hydrazine is used up, the remaining chlorite reacts with formation of ClO2.
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Thank you again for the experiments and reports...with such a fast follow up.
The EDA chlorite or EDA dichlorite are indeed very interesting.
They may be hygroscopic at least EDA monochlorite (I doubt EDA dichlorite will be).
Thanks to the high enough pKa of chlorous acid, evaporation into plain air is no troubles (CO2 can't displace it); so the salt(s) must remain integer.
Since the salt(s) are unknown or little studied better be cautious...if perchlorates are sensitive to shock, heat and friction (I have made N2H5ClO4
and EDA diperchlorate into the 50g range and those are not to worry so much about)...following books chlorates of organic amines are even worst (I
have never made any organic amine chlorates so I am of no help and I have no feeling to share about it)...
Chlorites may (or not) reveal to be even less stable...hard to predict...so better avoid glass.
Your experiments with chlorites and amines are very interesting!
They prove that:
1°)chlorite anion is more reactive/oxydizing into acidic media which can be direct acid or discrete acid like into an acidic salt (hydrazine
hydrogenosulfate or hydrazinium chloride) or a salt of a weak base (mild acid).
2°)chlorite seems stabler into basic media like organic amines.
You potentially made hydrazinium chlorite and EDA chlorite/dichlorite.
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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