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User
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This is most interesting.
Too bad that no exact procedures or tests are described.
Anyone willing to test this ?
Also this makes me wonder if a perchlorate form would be of any interest.
[Edited on 5-9-2009 by User]
What a fine day for chemistry this is.
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Taoiseach
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Fascinating stuff. The patent is quite vague tough. Here's the relevant info I scraped together: "Usually, one molecule of neutral chlorate of lead,
one molecule of glycerine, or mannite or of any other polyatomic alcohol, and one molecule of plumbic oxide or hydrate respectively are caused to
react [...] Likewise, a solution of bibasic or tribasic acetate of lead gives instantaneously in presence of a readily soluble chlorate, such as
chlorate of soda, of calcium, of magnesium or of ammonium, or by addition of alcohol, with mannite, mannitan or even wih glycerin, fluminating
compounds".
Due to its insolubility (0.037/100g H2O @ 20°C) Pb(ClO3)2 should precipate from hot solutions of KClO3/NaClO3 and any soluble lead salt.
A somehow related tidbit of info from the E&W board:
"Lead glycerolate can be done by boiling excess glycerol with lead hydroxyde (1/2hour)
CH2OH-CHOH-CH2OH + Pb(OH)2 --> CH2OH-CH(O-)-CHO-Pb + 2 H2O
Filtrate the white precipitate (Pb(OH)2 is also white so it appaers nothing has happened but stil) wash with water several times and allow to dry at
40-60C.
The dry compound deflagrates when heated confined."
This must be related somehow, maybe the chlorate complexes actually being double salts of lead glycerolate and lead chlorate.
A similar double salt forms from lead acetate and lead perchlorate.
There's plenty of info on metal glycerolate complexes:
BRYLANTS, J and PHILLIPPE, A N (1980). IR and moessbauer study of
iron glycerolates. J. Inorg. Nucl. Chem., 42(11): 1603-1611.
GADD, K F (1981). Complexes of copper (II) with polyhydric alcohols.
Educ. Chem., 18(6): 176-178.
HAZIMAH, A H (1998). Characterization and reactions of copper (II)
glycerol complex. Ph. D. thesis. Universiti Putra Malaysia.
HAZIMAH, A H; KAREN ANNE CROUSE; BADRI, M; CHONG, F K and
ABDUL RAHMAN MANAS (2000). Isolation and characterization of
copper (II) glycerol complex. Malaysian Journal of Chemistry No.1:
008-0011.
KOYANO, H; KATO, M and TAKONOUCHI, H (1992). Electrodeless
copper plating from copper-glycerin complex solution. J. Electrochem.
Soc., 139(11): 3112-3116.
NAGY, L; BURGER, K; KURTI, J; MOSTAFA, M A; KORECZ, L and
KIRICSI, I (1986). Iron (III) complexes of sugar-type ligands. Inorg.
Chim. Acta., 124(1): 55-59.
RADOSLOVICH, E W; RAUPACHI, M; SLADE, P G and TAYLOR, R M
(1970). Crystalline cobalt, zinc, manganese and iron alkoxides of
glycerol. Aust. J. Chem., 23: 1963-1971.
TAYLOR, R M and BROCK, A J (1989). Zn glycerolate complex. US
Patent 4 87 378.
I wonder if similar complexes of copper, iron or nickel exist.
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woelen
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I retried the experiment of Taoiseach and now I had partial success. I took some copper sulfate and dissolved this in 12% ammonia, I added just enough
ammonia to get all of the copper sulfate dissolved. This gives a deep blue solution. To this I added a few drops of highly concentrated solution of
sodium azide. When this is done, the color remains deep blue.
Then I added 96% ethanol, approximately the same volume as the deep blue aqueous solution. Again, this results in formation of a purple/blue
precipitate. This time, however, did not keep the precipitate, but the liquid. Once the precipitate had settled at the bottom, the liquid had a
green/cyan color and it was fairly dark. This liquid was allowed to stand for many days. After several days, a crop of nice green glittering crystals
was at the bottom of the test tube. These crystals were put on a piece of filter paper, in order to absorb most of the liquid and the crystals were
allowed to dry in a warm place in a petri dish for a few hours.
The dry material consists of many small needle-shaped green crystals, some of them glittering very nicely. The material looks nice. Some of these
crystals were put on the tip of a screw driver and this was put in a flame. The result is a soft crackling noise and many little sparks are created.
Some larger crystals give a somewhat louder PENG sound, but not an impressive bang. Most beautiful, however, is the color which is given to the flame.
When a crystal of the material crackles, it produced many fine particles, which give a beautiful green color to the flame of the alcohol burner. This
is due to the copper content of the particles.
So, again, I did not get the heavy bang explosive, but the material I obtained was cute and had funny properties. My conclusion, however, is that
making the ammonia/azide complex of copper(II) is not that easy, one easily ends up with other compounds.
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Formatik
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lead oxohalogenates
Note that Pb(ClO3)2.H2O is actually very soluble in water (see Mellor, et al.), the compd. is deliquescent. There is conflicting data on alcohol
solubility; whereas in Mellor it says alc. precipitates it, Wächter (J.pr. 1843, 30, 329) says it is "very easily" sol. in both water and alc.
The lit. methods of preparation go off from dissolving PbO in calculated amounts of aq. chloric acid. If Wächter is right then one might be able to
make it by combining aq. Pb(NO3)2 and NaClO3 and then separating by ppt. the NaNO3 with alcohol (at 70 wt.%, rest water not more than 7.81g NaNO3
dissolves per 100g), cryst. impure chlorate.
The monohydrate itself can explode if heated quickly to about 235º (Wächter just described vigorous dec. under sizzling), at 150º there is 4.59%
water loss. Pb(ClO2)2 is also explosive and was briefly mentioned in this thread.
[Edited on 6-9-2009 by Formatik]
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PHILOU Zrealone
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Quote: Originally posted by Taoiseach  |
A somehow related tidbit of info from the E&W board:
"Lead glycerolate can be done by boiling excess glycerol with lead hydroxyde (1/2hour)
CH2OH-CHOH-CH2OH + Pb(OH)2 --> CH2OH-CH(O-)-CHO-Pb + 2 H2O
Filtrate the white precipitate (Pb(OH)2 is also white so it appaers nothing has happened but stil) wash with water several times and allow to dry at
40-60C.
The dry compound deflagrates when heated confined."
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Looks familiar to me... as I was the writer 
As mentionned the white Pb(OH)2 is hard to distinguish from the glycerolate as its displays the same colour.
The compound is not very impressive: when dry and in contact with a flame in the open, it puffs like does the Ag oxalate, but under confinement of an
aluminium foil and if warmed, it explodes mildly.
Maybe with glycol in place of glycerol, one would add a bit more to the explosive power.
Lead chlorate will add oxygen to the stuff en renders it more energetic. Although I wonder if a simple mix of Pb(ClO3)2 and polyol co-cristallised
will not do as good...because Pb(ClO3)2 being detonating stuff on its own in a chlorate/sugar like composition must be quite powerfull.
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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Taoiseach
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Wikipedia once again proved guilty of spread of bullshit and disinformation  Yes
Pb(ClO3)2 is highly soluble. I suppose there's no easy way to obtain it from soluble chlorates.
Dilute solutions of HClO3 can be made from oxalic or tartaric acid and KClO3. Potassium hydrogen tartrate/oxalate is highly insoluble.
I found a procedure on a German forum - basically 14,5 grams of KClO3 are dissolved in 70ml H2O @60°C. Another solution is prepared from 17,8grams L+
tartaric acid and 30ml H2O. These solutions are cooled to 10°C and poured together to yield ~10% HClO3 and insoluble K tartrate which is then removed
by filtration. It obviously works. Of course this says nothing about the purity of product . Then again why give a shit about purity when the aim is
to make some esoteric stuff that we don't even know the composition of.
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Formatik
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lead bromate
Pb(BrO3)2.H2O is much less soluble than the Pb(ClO3)2 salt according to Mellor, so it shouldn't be too hard to collect from NaBrO3 and Pb(NO3)2 aq. It
might build similar complexes, but who knows I can't determine it at present.
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chloric1
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| Quote: Originally posted by Taoiseach | Wikipedia once again proved guilty of spread of bullshit and disinformation Yes
Pb(ClO3)2 is highly soluble. I suppose there's no easy way to obtain it from soluble chlorates.
Dilute solutions of HClO3 can be made from oxalic or tartaric acid and KClO3. Potassium hydrogen tartrate/oxalate is highly insoluble.
I found a procedure on a German forum - basically 14,5 grams of KClO3 are dissolved in 70ml H2O @60°C. Another solution is prepared from 17,8grams L+
tartaric acid and 30ml H2O. These solutions are cooled to 10°C and poured together to yield ~10% HClO3 and insoluble K tartrate which is then removed
by filtration. It obviously works. Of course this says nothing about the purity of product . Then again why give a shit about purity when the aim is
to make some esoteric stuff that we don't even know the composition of.
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You will need to filter with mineral wool, glass wool etc. IIRC filter paper soaked in chloric acid ignites. It would be adviable to recrystalize
the lead chlorate you would form. Maybe a water/alcohol mix 1:1 would suffice.
Fellow molecular manipulator
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Taoiseach
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I never heard that filter paper soaked in 10% HClO3 ignites and I highly doubt it would. The concentrated acid is very dangerous yes, but don't shit
your pants about something as dilute as 10%.
Of course Ba(ClO3)2 + H2SO4 will give a product of higher purity and concentration. The advantage of the above procedure is that the precursors are
easier to come be. KClO3 can be made by electrolysis and tartaric acid is a common food additive and doesnt raise any suspicion when ordered in a
drugstore.
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Rosco Bodine
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| Quote: Originally posted by Taoiseach |
Dilute solutions of HClO3 can be made from oxalic or tartaric acid and KClO3. Potassium hydrogen tartrate/oxalate is highly insoluble.
I found a procedure on a German forum - basically 14,5 grams of KClO3 are dissolved in 70ml H2O @60°C. Another solution is prepared from 17,8grams L+
tartaric acid and 30ml H2O. These solutions are cooled to 10°C and poured together to yield ~10% HClO3 and insoluble K tartrate which is then removed
by filtration. It obviously works. Of course this says nothing about the purity of product . Then again why give a shit about purity when the aim is
to make some esoteric stuff that we don't even know the composition of.
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Neutralizing the so obtained 10% HClO3 with glycine or betaine should provide the corresponding organic chlorate salt, and these salts should be
highly energetic materials
of possible interest gotten via a relatively mild and mundane synthetic route.
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[Edited on 11-9-2009 by Rosco Bodine]
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TechnologicallyRetarded
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Lead Salt Solubility Info.
I'll take this opportunity to post this link to the 'The lead salts preparation thread!'....
http://www.sciencemadness.org/talk/viewthread.php?tid=5490
This may all be known to you, I haven't read through this entire thread yet. Please don't flame me (again), I'm still getting used to the skin-grafts
from last time.
Basically:
Pb(ClO3)2.0H2O - 144 @ 18C (vs in EtOH)
Pb(BrO3)2.1H2O - 1.33 @ 20C
Pb(IO3)2.0H2O - 0.0025 @ 25C
Pb(ClO4)2.0H2O - 441 @ 25C (s in EtOH)
All the above info was nicked from the other thread.
Tr
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TechnologicallyRetarded
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... Just edited the solubility of the Chlorate on wiki.
And Rosco, that's some trippy music... not sure if I like it or not. ; )
Tr
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Rosco Bodine
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The lead chlorate can form by double decomposition from lead nitrate and potassium chlorate when the lead chlorate is precipitated as an inclusion in
a low solubility salt such as a clathrate type quasi-multiple salt. There is always the possible unpredictable formation of possible double salts or
multiple salts which can complicate matters, or can produce different results depending upon temperature and concentrations. Wife swapping,
threesomes....who knows
for certain what may happen in an untested mix of reactive components where the unexpected anomaly may be lurking 
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http://www.youtube.com/watch?v=mW2R2zAVGVY&fmt=18 Bliss - Kissing
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TechnologicallyRetarded
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Hexamine complexes?
I've done some research into Polyol complexes, I don't know if we'll win this battle. The complexes consist of deprotonated polyol species, usually
adjacent groups. For instance, when glycerol form's complexes, they consist of -OCH2CH(O-)CH2OH groups. This leaves no room for other anions... does
it?
But Hexamine complexes however...
| Quote: |
The 3CuCl2·4hmta·2HCl·2H2O complex (hmta=hexamethylenetetramine) has been obtained from acid solution. Spectroscopic and magnetic investigations
indicate that, in the crystal structure of this compound, the polymeric chains, 3CuCl2·2hmta·2H2O, and hmta·HCl groups occur.
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... may be promising.
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Formatik
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more info on some lead salts
After some more digging, I found out Pb(BrO3)2.H2O has some energetic properties itself also (easily explodes if it attempting to dry it by heat). It
also forms complexes, e.g. preparation of it using lead acetate isn't recommended since lead(II) bromate-acetate (highly expl.) can form. The lead
acetate-bromate complex already has its own thread here.
Some other complexes are basic lead (II) chlorate-acetates: Pb2(OH)(ClO3)2CH3CO2.2.5H2O detonates with loud bang if dry heated.
Pb3(OH)2(ClO3)2(CH3CO2)2.3H2O on dry heating, explodes with a large brisance. Various lead(II) acetate-perchlorates which all explode on impact or by
heating. Lead (II) perchlorate-oxalates, e.g. [Pb2(C2O4)](ClO4)2.3H2O is said to only deflagrate weakly when heated.
Lead chlorite-formate Pb(ClO2)(HCO2), unstable at regular temps., yellow compd. made by digesting a cold and quickly precipitated Pb(HCO2)2
precipitate with a NaClO2-solution (in excess of up to 50%), then washed with alcohol and ether. It discolors brown in a few hours. No energetic
props. mentioned of this compd, but it could have some.
Attachment: Pb(BrO3)2.pdf (1.1MB)
This file has been downloaded 1378 times
Attachment: Pb(ClO3)2 no.1.pdf (1.7MB)
This file has been downloaded 1129 times
Attachment: Pb(ClO3)2 no.2.pdf (882kB)
This file has been downloaded 1234 times
Attachment: Pb complexes.pdf (1.7MB)
This file has been downloaded 1862 times
Attachment: Pb comp2.pdf (511kB)
This file has been downloaded 1277 times
[Edited on 30-9-2009 by Formatik]
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chloric1
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My understanding of German is a bit sketchy. But I caught a route to synthesis by PbSO4 and KClO3 ! Most lead sulfate I would have would be waste from lead(II) reactions! I cannot recall to what extent but I do
know that lead sulfate is considerably more soluble in water than the carbonate. Of coarse pretty dilute solutions(lesss than 10%) would be needed.
Come to think of it, the reaction could be easily reversed so it might be better to work with 80% alcohol solution in water instead of pure water. I
also seed that the crystline habit is monoclinic prisms. A beautiful sight to behold for sure!
Fellow molecular manipulator
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Taoiseach
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@Formatik
thx for the interesting upload. From which book are these excerpts?
I feel some misgivings now about the possible tartaric acid + KClO3 route to lead chlorate. Quite possible that a dangerous tartrate-chlorate double
salt would form.
What remains to be investigated is the insoluble clathrates of lead chlorate, e.g. a solution of sodium chlorate, lead acetate and glycerine should
yield such a compound after addition of ethanol. That'd be an interesting novelty to fiddle with - no fancy chemicals required. Anyone dare to try?
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Formatik
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Gmelin
They're from Gmelin's Handbuch der anorganischen Chemie. Basically it's a huge set of books found at decent libraries. I believe Beilstein
Crossfire also gives access, but I've never set out to use it.
Btw, calcium oxalate is many times less soluble than potassium bitartrate. It's said though its sol. increases in strong acids, when I prepd. HClO3
using impure Ca(ClO3)2 (HClO4 thread), most to near all oxalate seemed to ppt. Using PbSO4 to prepare the chlorate looks like a pain, Gmelin mentions
formation from boiling PbSO4 in KClO3 soln. citing the Ann. Chim. Phys. ref.
And a quick comment about HMTA complexes above. Although nitrogen containing, I doubt they show much interest because the energetic aspect may be
muffled by the high oxygen imbalance. Like with the divalent metal hmta.persulfates, no energetic properties were noted in the journal cited earlier.
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Pope
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Is there a metathesis process I can use with KNO3 and Copper ******? to get copper nitrate?
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User
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Wrong topic, dumb question...?
What a fine day for chemistry this is.
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Pope
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Yea it is a dumb question cause it most probably has been answered god knows how many times, but it still has relevance that comes back to this
initial thread and I thought that by posting here and not necro posting or making a new thread just to ask a simple question so I posted here
expecting someone to understand, I guess not sorry.
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Evilblaze
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Hydrazine hydrate copper perchlorate complex
Yesterday I made a complex salt. On the forum it was previously mentioned, that this complex exist, but there was nothing else wrote from it. I found
some information in: Encyclopedia of Explosives and Related Items - Fedoroff - Vol 7 of 10, but there was also just written, that this compound exist,
but no other information.
The complex was prepared by the following way: a freshly prepared solution of copper perchlorate (from copper sulfate and sodium perchlorate) and
hydrazine hydrate solution was reacted with each other and a brown precipitate formed. It was filtered and washed with water.
The brown precipitate when heated decomposes slowly and thus can be easily dried. It detonate when contact with flame. It can not be stored it
decomposes to nitrogen, water and copper perchlorate. After 4 hour storing the compound, the copper-perchlorate-s blue color can be seen on the top of
the complex.
Anyone got idea to a stable hydrazine-metal-perchlorate complex? The nickel salt detonates immediately. Maybe I will try the complex with Cd, Zn
perchlorates.
I upload a video from this complex when it is ignited by flame.
Attachment: hydrazine-hydrate-copper-perchlorate complex 1.wmv (1.5MB)
This file has been downloaded 1553 times
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Taoiseach
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Interesting... nice video thx.
I have never heard of any other stable complexes of this kind. You should be VERY careful when you experiment with hydrazine perchlorate complexes as
the stability seems to depend on crystal size and/or modification. The poor guy who made nickel hydrazine perchlorate first isolated a small amount of
the dry crystals and didn't find them to be very sensitive. The next batch however exploded when he stirred the solution. Scary stuff 
[Edited on 12-11-2009 by Taoiseach]
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Taoiseach
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Nitroaminoguanidine was mentioned here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=81...
It is a condensation product of hydrazine and nitroguanidine. Due to its low O content its probably not very energetic. However its ease of
preparation and its many nitrogens with unpaired electron pairs gave rise to the question if it could find use as an energetic fuel kind of ligand in
coordination complexes.
I prepared a small batch following patent US2617826. This procedure was originally posted by Sobrero:
14g hydrazine sulfate and 8g NaOH were dissolved in 100ml warm water. This was added to a suspension of 11g nitroguanidine in 150ml boiling water. The
solution was then hold at 80-90°C and stirred vigorously until all nitroguanidine had gone into solution. The liquid was colorless at first, then
slowly turned yellow and finally deep orange.
The solution was then neutralized with conc. HCl while still hot, and then cooled in an ice bath to around 5°C. About 7.5g of pale yellow crystals
were obtained. Note: Using less dilute solutions might give higher yields.
The lead and copper salts were prepared as follows:
Pb(NAG)2:
1g NAG was dissolved in 30ml of hot water (85°C).
1g Pb(OH)2 (prepared by adding 0,5g NaOH to a hot solution of 1,4g Pb(NO3)2) was added and the mixture stirred well. Upon cooling, yellow crystals
formed slowly; these were pressed dry on a filter paper and dried with warm air from a heat gun.
Cu(NAG)2:
1g NAG was dissolved in 25ml of hot water (85°C).
1g CuSO4*5H2O in 10ml hot water was added, followed by 1g NaOH. The mixture was stirred well, filtered and the crystals dried with warm air.
NAG just flares upon ignition whereas the lead salt gives a pop sound similar to Pb(C6H2N3O7)2 in small amounts. The Cu salt is less energetic.
I then tried to make [Cu(NAG)2](ClO4)2. Papers on the nickel nitrate/perchlorate complexes are available in references section and suggest NAG acts as
a bidentate ligand.
No measurements were made this time. A few mililiters of perchloric acid were neutralized with CuCO3. The liquid was filtered and a solution of NAG in
80°C water was added dropwise. The solution turned a deep blue color, not unlike an ammoniacal complex. Upon cooling in the freezer glistering blue
crystals were obtained. These were carefully pressed dry on filter paper and dried with warm air, then dried over NaOH (to remove excess HClO4).
Trying to obtain a further crop by adding an equal volume of EtOH did not yield the complex but pale blue crystals of pure Cu(ClO4)2.
Upon ignition, the complex deflagrates violently. Its ability to make the DDT in very small amounts is comparable to NHN (nickel hydrazine nitrate) if
not even better. Tightly wrapping 50mg in a few layers of aluminium foil and heating on a bunsen burner caused detonation. A quantity amounting to 1/4
of a matchhead was placed on concrete floor and given a good smack with a hammer and the resulting pain in the ears suggested its very energetic  The crystals are perfectly dry, nonhygroscopic and air stable. Quite encouraging so
far.
I also attempted to make [Cu(NAG)2](BrO3)2. A solution of copper bromate was prepared from barium bromate and copper sulphate. This was evaporated
until a saturated solution of about 80°C was obtained. A solution of NAG in 80°C water was added with stirring. Complexation was evidenced by a deep
blue coloration but the color quickly faded away. Effervescence was noted (O2 or CO2?) and the solution turned a pale green, also a faint smell of
bromine was noted. I figure the bromate oxidized the NAG in solution. At a lower temperature the complex might persist tough.
(Left to right NAG, NAG-Cu, NAG-Pb, [Cu(NAG)2](ClO4)2
[Edited on 15-1-2010 by Taoiseach]
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chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
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Very nice!
I don't like the method of drying the sample with NaOH (to remove HClO4), at least use KOH!
Why do you need 80 deg C for reaction (complexation) of NAG with copper perchlorate?
Impressive that the Cu-NAG-ClO4 crystals are stable at air! That is very unusual!
Pb(C6H2N3O7)2 - please clarify for the uninformed what it is.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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