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Ramiel
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[*] posted on 31-8-2002 at 22:49
perchloric acid


Robinson reported a detonation of 3 g of a Perchlorate salt of a rhodium-polyamine complex undergoing an evaporation step in a rotary evaporator. A violent explosion destroyed the evaporator, smashed a lab jack, cracked the bench top, and chipped walls over 15 feet away. Fortunately, this happened in an empty laboratory.

If that isn't energetic, then what is!

by the way, would this reaction work?
KNO3 + HClO4 <==>> HNO3 + KClO4
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[*] posted on 1-9-2002 at 10:43


Yes, that reaction will work, but it will tend towards the nitric acid & ptoassium perchlorate side, because potassium perchlorate is less soluble than potassium nitrate.

Who the fuck is Robinson?

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[*] posted on 1-9-2002 at 11:37


Well, I can imagine Rhodium complexes do not have strong bonds. Also, Rhodium, being a noble metal, would like to return to it's elemental state when heated.
Add to that a perchlorate group which is eager to oxidize the partially radicalized (because the Rhodium decomplexes) amines and you've got a nice bang!

Not a smart move, heating perchlorate esters.




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[*] posted on 1-9-2002 at 11:40


Not a smart move, heating perchlorate esters.

That should say: Not a smart move, heating organic perchlorate compounds.




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Ramiel
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[*] posted on 2-9-2002 at 05:56


Quote:

Also, Rhodium, being a noble metal,

If Rhodium is noble, then how does it display metallic properties?

ps. So, it does work, and it is an equilibrium reaction, tending towards the KClO4 side...
Now theoretically one might obtain a good yeild by extracting th precipitate KClO4 as it formed.

Now to get rid of the HClO4... it reacts with silver I believe, so a little chunk of that would absorb the excess, but it is expensive, any other method(s) for getting rid of the excess KNO3 and HClO4?
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[*] posted on 3-9-2002 at 01:34


?

Rhodium is a metal, look it up?

And what are you babbling about in the last paragraphs of your posts?




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[*] posted on 3-9-2002 at 01:39


Wow sorry. Missed something there.:(

Why would you want to get rid of the HClO4? HClO4 is a very strong acid, it easily reacts with KOH, etc....

Rhodium conducts electricity, has a very high melting point and it is a Platinum metal. It's in group 8b of the Periodic table.




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Ramiel
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[*] posted on 3-9-2002 at 02:11


I got confused; you were talking about it being a noble metal. Please remember that in year twelve chemistry, we still treat metals like Au and Rh as reactive, But now I understand (my chem teacher is 1337)

This has veered a little off the topic, but;
Quote:

Why would you want to get rid of the HClO4?

because I want to make KClO4 - which is the product of the forward reaction. Although HNO3 is a by-product, but I'd like to keep it if possible.

Quote:

it easily reacts with KOH

So does HNO3.
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[*] posted on 3-9-2002 at 05:58


what do you plan to do with the KClO4? just use it as an oxidiser? if you want it for HE mixes just make NH4ClO4. it is far superior

HClO4 + NH4OH = NH4ClO4 + H2O

and if you want to make HEs why dont you make something a little more exotic? if you are crazy you can go for organic perchlorates. these interest me.




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Ramiel
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[*] posted on 5-9-2002 at 00:59


I've heard it makes a "/\/\4D" oxidizer for flash mixtures.

Oh, and I've been looking at "RDx"
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[*] posted on 5-9-2002 at 07:48


The problem with making organic perchlorates is that there are some very unstable intermediate compounds or byproducts. Also, temperature control is EXTREMELY important because perchloric acid will ignite anything flammable.

So you better stay well below the flashpoint of your organic.




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[*] posted on 9-9-2002 at 16:04


As explained elsewere transition metals often forms complexes with pi electron donor ligands (complexants)...amines, amonia, urea, hydrazine, ethylene diamine...the counteranion can be a strong oxydiser like Cr2O7(2-), SO5(2-), NO2(-), NO3(-), ClO4(-), IO3(-), MnO4(-), ....the fact it is a complex lower strongly the activation energy and this explains why
Cu powder and KMnO4 can sensitise AN!
TACuN and other are sensitive HE...some complexes are so unstable that they are touchy sensitive even in solution; it is the case of Ni(NH2-NH2)3(ClO4)2 that explodes in diluted solution when agitated!

Ni(NH2-NH2)3(NO2)2 is one of the best primaries I have ever made:
VOD = 7km/s, quite unsensitive to shock very sensitive to flame, unsoluble in water!
The sole problem is that you need pure NH2-NH2 hydrate!Deflagrate in the open or in tiny amounts and detonates strongly when confined.

PH Z
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[*] posted on 9-10-2002 at 15:55


Philou, how did you prepare Ni(N2H4)3(NO2)2?

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cool.gif posted on 5-3-2003 at 02:32


Ni(NH2-NH2)3(NO3)2 is fairly easy to do:
Make a mix of saturated Ni(NO3)2 in water add twice the amount of ethanol; you get a green solution.
Make a saturated solution of hydrazine hydrate in ethanol (50/50)!

Then allow the first one to fall drop by drop in the other under magnetic agitation...until no more precipitate forms!


You will see deep blue flocks form those will break under the agitation and turn pale pink; then when reaction is ended (it heats a little during complexation) filtrate the precipitate...you will be estonished how much there will be!
Wash it under cold distillated water first (insoluble in water), filtrate; then wash with ethanol, filtrate and dry in open air ...you get a white pinkish powder/or like cley blocks.

You can grind them smoothly to make it loos!

This stuff is powerful and deflagrate when in the air in large amount ( over 2g); when confined 0,5g will detonate in Al foil wrapped chunk trowed in an open fire... beware the fire ball can be 40 cm diameter and trow burning wooden pieces all over the place!

That's it man!
It is more powerful than other primaries, but if in tiny amounts the detonation rate is irregular!
I have solved that problem; it is one of my discoveries, and I'm very proud of it.... I use Ag2C2.2HNO3!
The two detonating substance are very unsoluble, don't react at ambiant T and they both provide the best of them to the mix!

Ag2C2.2HNO3 easy to make, easy detonation even unconfined, powerfull and fast!

Ni(NH2-NH2)3(NO3)2 easy to make, detonate only when confined or in large amount, much more powerfull, brisant and faster!

About the rest of the answers, I have many things to say:

Making organic perchlorates is easy especially amines perchlorates (as soon as you are dilluted enough no risk due to heat when neutralising); beware of transition metals that may form complexes upon contact!

Making complexated perchlorate is much more dangerous; some detonate while solution is agitated!

Making organic ester perchlorate is foolish too: they inflame or detonate spontaneously at 20°C and are all very sensitive!

Rhodium belongs to the platinium familly of noble metal; but noble means rare and hard to oxydise; it doesn't mean unreactive like the noble gases..rhodium was named because of the color of its salts...thus it makes salts much more easily than Au or Pt does!
The whole familly also has the property to complexate ligands!I have worked many times with Ruthenium for my study endwork!

KNO3 + HClO4 --> KClO4 + HNO3 (heat at 90°C on water bath and collect the condensed HNO3).

The reaction is favourised by many more factors:
*HClO4 is 4 000 000 times more acidic than HNO3 thus NO3(-) is the same time much basic than ClO4(-)
*KClO4 is less soluble than KNO3
*HNO3 is more volatile (much lower BP) than HClO4.

Rotary evaporator are used to draw off solvant under reduced pressure and normal temperatures...For sensitive compounds it is the best; but if the stuff cristallised in the flask, and that he did this cristals might frictionnate each other in the flask while rotating...maybe he did heat it too strongly...those complexes of noble metals are quite heat sensitive and decomplexate or react when over heated (over 40°C).

The guy probably never made any small test on the stuff prior to experiment to evaluate risk or didn't knew about explosivity of perchlorate complexes (what means he asn't informed before acting).




PH Z (PHILOU Zrealone)

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[*] posted on 5-3-2003 at 12:09


Quote:
Ag2C2.2HNO3 easy to make, easy detonation even unconfined, powerfull and fast!

Is this as simple as it sounds - i.e. combining Ag2C2 and HNO3 in a 1:2 ratio? What about sensitivity to heat, impact, friction, static, etc.? Can you prepare Cu2C2.2HNO3 similarly, and does it behave similarly?
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[*] posted on 6-3-2003 at 11:00


Silveracetylide-nitrate can be made by bubbling acetylene through a solution of silver in nitric acid ( where Ag2C2 is made by bubbling C2H2 through AgNO3 in ammoniacal solution ).
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[*] posted on 6-3-2003 at 11:14


all carbides reacts with acids yielding
hydroxide and C2H2, some takes strong acids (Cu2C2, Ag2C2) some it only needs water...

/rickard
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[*] posted on 6-3-2003 at 11:29


Actually these which are before the H in the activity series (na, Ca, etc) are decomposed by the water with the formation of acetylene, and ethane. Al4C3 i.e. needs HCl because to disolve the Al2O3 formed in the reaction with the water in order to give ethene. These carbides are stable in temperature. Carbides after the H are unstable in elevated temps (explosives) but stable in water.


Philou, have you ever cosidered to write a book (I mean a small file) about your experience in the field ? I bet it'll be the best one. And it's pitty if you don't write one.
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cool.gif posted on 23-3-2003 at 15:30


Ag2C2.xHNO3 only forms when C2H2 is bubbled into neutral or slightly acidic AgNO3 solution!
H-C#C-H + 2AgNO3 --> Ag2C2 + 2HNO3
And HNO3 is trapped/complexed in the solid precipitate that flocculates!
It seems very unprobable HNO3 can be added to a precipitate of Ag2C2 in an efficienter way than when it does in precipitation process!
The amoniacal process is harder and leaves residual Ag-NH2 (hell of the mirror makers) that explodes in solution; this not only increases sensitivity to heat, impact and light! Density is about the same but VOD of nitrated complex is about twice the one of the one from ammonia! Thus there is no reason to make Ag2C2 instead of Ag2C2.xHNO3

This gives me an idea!
C2H2 + AgClO4 --> Ag2C2.xHClO4
For sure this must be a little more powerfull and maybe a bit more sensitive!

Cu2C2 is not a stable carbide it fast disproportionnates in water to give CuC2 + Cu that has about the same colour and no explosivity! I don't think a similar nitrate complex exists...but I haven't ever tried! The fact is that you need to make CuCl in ammonia to allow the making of Cu2C2; CuNO3 doesn't exist long enough in water to react!

Hg2C2 is also a powerfull explosive of similar properties as Ag2C2 plus the fact that Hg can be gaseous product (high volatility).

Al4C3 reacts with water to provide CH4 not C2H2! Na2C2, K2C2, Li2C2, BaC2, CaC2 and SrC2 provides C2H2!
Fe4C3 is stable and responsible of the hardness of iron steel!

To write a book is hard work and I have the project to do so for nearly 10 years; but I need to gather info's and make more experiments to have something really complete and professionnal! One of the major investissement I have to do is to buy a portable power G4 (60 gigas, DVD and CD writer) this would allow me to go to the library and make a good data base about all articles about HE from my digital cam without passing by the long and expensive photoprinting of all books/articles!
Also to have articles is a thing; to read them, understand their meaning and the application of them is another; then summarize and integrate that in the good chapter and make a complete master piece!
:cool::):cool::D:cool:;):cool::o:cool::P:cool:




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sad.gif posted on 23-3-2003 at 15:36


I forgot to tell that the guy that had that accident maybe forgot that the ammonia complexes of those noble metals, not only are heat sensitive but also light sensitive! They display very dark colour and catch nearly all light that passes trough them to convert it into Infrared.Light induces ligand splitting and destabilisation of those complexes!

:cool:




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[*] posted on 25-6-2009 at 10:11


Hello,
Attached is some info. on Perchloric acid from the Bereau of Mines taken from http://www.hathitrust.org/.
Happy reading.
Dann2



Attachment: Perk. acid info.zip (1.2MB)
This file has been downloaded 212 times

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[*] posted on 25-1-2012 at 19:27



Can anyone tell me if I were to make some Perchloric acid from HCl (conc) + Sodium Perchlorate with a small amount of Chlorate contamination would the Chlorate present much of a hazard.
Would I not just get some ClO2 going off.
It will be in a well ventilated area, do not intend to concentrate or store the Perchloric acid (will dilute once made to 20% or so).
The Chlorate contamination is approx. 0.003% (1 gram per liter of concentrated Sodium Perchlorate solution or one gram in 500 grams approx.

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[*] posted on 26-1-2012 at 04:40


Quote:
Can anyone tell me if I were to make some Perchloric acid from HCl (conc) + Sodium Perchlorate with a small amount of Chlorate contamination would the Chlorate present much of a hazard.

It's been a while but using a large excess of HCl will decompose any NaClO3 in the perchlorate . . .
The fumes will be orange coloured and the reaction vigorous!
I know from experience that inhaling the fumes is less than pleasant.
But the small amounts of chlorate contaminant you have shouldn't be a problem!
The reaction itself is exothermic enough to ignite sugar/chlorate mixtures!
Distill off the HCl and stop when dense white vapour appears in the flask and you're done.
The minute quantity of NaClO4 remaining in the acid can be disregarded!
Distillation of the HClO4 you'll have shouldn't be attempted for obvious reasons!

[edit]
Chill the solution after the addition to precipitate all the NaCl; the longer you leave it, the better, and then filter . . .

P

[Edited on 26-1-2012 by Pulverulescent]
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[*] posted on 29-1-2012 at 10:18



Thanks for that.
I got around to doing it.

Added 750ml conc. HCl acid to 500ml of a saturated solution of Sodium Perchlorate of density 1.62
(about 520 grams Na Perchlorate). Temperature of solutions was around 8C.
Thats around 4.25 moles of Na Perchlorate which is 4.25 moles Perchloric acid = 426 grams (100%
acid) = 592 grams of 72% acid = 365ml of acid (density = 1.62 approx. read from graph) to be expected .
I ended up with 352 grams of 72% acid.



The Perchlorate contained about 2 grams Chlorate. The solutions warmed very slightly when mixed
and I obtained an immediate fine ppt of Sodium Chloride. The solution was yellowish. Let it sit for
about three hours and put in freezer for another three hours and filtered through a 15cm paper filter.
Obtained about 900ml of a yellowish liquid. Would have got more if I had suction filtered as
there was a large volume of wet NaCl.
Placed into a one liter beaker and boiled (outside) using a flame and a sand bath. At the beginning
the fumes were of HCl acid. When the volume was around 480ml the fumes were quite mild, temperature
around 130C. The colour of the liquid was still yellow but I think it was the sand underneath the beaker
that was making it look more yellow than it actually was . Boiled on until there was white fumes coming and
then boiled some more. I guess I boiled too much as I ended up with only 220ml. The temperature reading
on the thermometer was 170C.

The colour of the Perchloric acid was very slightly yellow at this stage but the HCl acid had a yellow tinge to it.

I let it cool and added 250ml water to it. The density of the acid is now 1.35g/cc. A concentration of
about 46% according to a graph. The acid looked much clearer the next day, very little if any yellow.





From Russion Journal:
Colourless perchloric acid, i.e. an acid containing no
lower oxides of chlorine, does not explode out of contact
with reductants, and is therefore safe when handled carefully.

Tested for Chloride using Silver Nitrate and there was none.
There is no sigh of any Na Perchlorate coming out of the acid when I checked two days later.

fumes.jpg - 47kB
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[*] posted on 29-1-2012 at 12:24


Dann, very nice, are you gonna make some organic perchlorate salt? If yes, try Biuret Perchlorate, in small quantity. It may be interesting.



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