| Pages:
1
2
3 |
Ramiel
Vicious like a ferret
Posts: 484
Registered: 19-8-2002
Location: Room at the Back, Australia
Member Is Offline
Mood: Semi-demented
|
|
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
|
|
|
IodineForLunch
Harmless
Posts: 34
Registered: 28-8-2002
Location: NJ
Member Is Offline
Mood: bored
|
|
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?
David Hansen
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
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.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
Not a smart move, heating perchlorate esters.
That should say: Not a smart move, heating organic perchlorate compounds.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
Ramiel
Vicious like a ferret
Posts: 484
Registered: 19-8-2002
Location: Room at the Back, Australia
Member Is Offline
Mood: Semi-demented
|
|
| 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?
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
?
Rhodium is a metal, look it up?
And what are you babbling about in the last paragraphs of your posts?
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
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.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
Ramiel
Vicious like a ferret
Posts: 484
Registered: 19-8-2002
Location: Room at the Back, Australia
Member Is Offline
Mood: Semi-demented
|
|
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.
|
|
|
Madog
Hazard to Others
Posts: 221
Registered: 20-5-2002
Location: USA
Member Is Offline
Mood: lysergic
|
|
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.
Most people outgrow their pyro tendencies, we are the ones who\'s tendencies outgrew us.
|
|
|
Ramiel
Vicious like a ferret
Posts: 484
Registered: 19-8-2002
Location: Room at the Back, Australia
Member Is Offline
Mood: Semi-demented
|
|
I've heard it makes a "/\/\4D" oxidizer for flash mixtures.
Oh, and I've been looking at "RDx"
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
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.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
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
|
|
|
IodineForLunch
Harmless
Posts: 34
Registered: 28-8-2002
Location: NJ
Member Is Offline
Mood: bored
|
|
Philou, how did you prepare Ni(N2H4)3(NO2)2?
David Hansen
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
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)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
|
|
|
Polverone
Now celebrating 21 years of madness
Posts: 3186
Registered: 19-5-2002
Location: The Sunny Pacific Northwest
Member Is Offline
Mood: Waiting for spring
|
|
| 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?
|
|
|
Microtek
National Hazard
Posts: 869
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
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 ).
|
|
|
rikkitikkitavi
Hazard to Others
Posts: 192
Registered: 17-6-2002
Member Is Offline
Mood: No Mood
|
|
all carbides reacts with acids yielding
hydroxide and C2H2, some takes strong acids (Cu2C2, Ag2C2) some it only needs water...
/rickard
|
|
|
a_bab
Hazard to Others
Posts: 458
Registered: 15-9-2002
Member Is Offline
Mood: Angry !!!!!111111...2?!
|
|
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.
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
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!
    
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)
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
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!
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)
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
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 669 times
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
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.
Dann2
|
|
|
Pulverulescent
National Hazard
Posts: 793
Registered: 31-1-2008
Member Is Offline
Mood: Torn between two monikers ─ "hissingnoise" and the present incarnation!
|
|
| 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 NaClO<sub>3</sub> 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 NaClO<sub>4</sub> remaining in the acid can be disregarded!
Distillation of the HClO<sub>4</sub> 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]
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
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.
|
|
|
Adas
National Hazard
Posts: 711
Registered: 21-9-2011
Location: Slovakia
Member Is Offline
Mood: Sensitive to shock and friction
|
|
Dann, very nice, are you gonna make some organic perchlorate salt? If yes, try Biuret Perchlorate, in small quantity. It may be interesting.
Rest In Pieces!
|
|
|
| Pages:
1
2
3 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
