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hissingnoise
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Try it with the sodium salt; it contains a higher percentage of oxygen (than the K salt) which makes the reaction more vigorous, presumably.
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Formatik
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| Quote: | Originally posted by hissingnoise
Try it with the sodium salt; it contains a higher percentage of oxygen (than the K salt) which makes the reaction more vigorous, presumably.
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Will have to make some NaClO3 and LiClO3 some time. The latter has more O: 53% vs. 45%.
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Formatik
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some more
Below are some reaction experiments of the strong oxidant nitrosyl perchlorate, albeit impure. The compound nitrosyl perchlorate also has its own
thread here. That's a good thread to look at about the compound. According to the lit. (e.g. Hofmann, Zedtwitz, Ber. 42, [1909] 2031) NOClO4 immediately
forms methyl nitrite with methanol; ethanol, acetone, and ether inflame or explode after several seconds.
Also reacts extremely violently with the primary amines of the benzene group: aniline, o- and p-toluidine, mesidine, xylidine, apparently so due to
intermediate diazonium perchlorates (extremely explosive compounds). Hofmann was able to prepare perchlorate esters from alcohols like glycol when the
reaction wasn't too violent. Urea and many other compounds also ignite or react similar. In Lehrbuch der anorganischen Chemie (1919) by Karl A.
Hofmann, he says the perchlorate is useful for a number of interesting demonstrations.
After prep. procedure from N2O3 and conc. HClO4, the NOClO4 couldn't be readily obtained anhydrous or acid-free and was mostly removed from the HClO4
by glass filtration. So in all attempts it was slightly moist with the HClO4, and the hydration water wasn't removed (NOClO4.H2O). Despite that some
test were done to see what happens. Anhydrous material should yield more spectacular results. It can be washed with dry nitromethane to remove the
acid, and then it can be dehydrated entierly by standing it with P2O5 in a vac. for a few days. Below was studied the reaction of only
the moist oxidant with: diethylether, dimethylformamide, dimethylsulfoxide, ethanol, methanol, toluene, o-tolidine, acetone, methylethyl
ketone, turpentine. Strongest reaction seen with the latter. The reactions likley become more violent if scaled up and with pure oxidant.
1.6g NOClO4 (so as said above, HClO4-moist) in a plastic cap had 5.1g anhydrous ether dumped in, when mixed there is a only very short delay in
reaction and then it begins boiling, formaldehyde smell is given off among fumes. Eventually it stops boiling. No other reaction after around 2
minutes and beyond.
0.2g NOClO4 in plastic covered metal cap, then 0.5mL DMF added. After 4 minutes no significant interaction. So it was left standing for several
minutes and eventually shaken, after which it began to give off a few bubbles and eventually quietly dissolved.
Small chunk of the NOClO4 maybe 0.2g on a flat surface with a few mL (maybe 0.4mL) 99% DMSO only frothed for some time.
In plastic cap, 0.4g of the NOClO4 had a few mL, maybe 0.5mL denatured alcohol dumped in, soon after the addition it started boiling, fruity
acetaldehyde smell given off.
Then 0.1g NOClO4 in a plastic cap had several drops of methanol dumped in at once, and it rapidly starts boiling when the methanol is added.
Maybe like 0.2-0.5mL of toluene added to 0.3g NOClO4 in a plastic cap. As soon as the toluene was added the white solid turned reddish orange, and
after standing long several minutes the solid turned a darker red-orange.
0.1g NOClO4 in a small cap, had a few drops o-tolidine added. As soon as a drop contacted the perchlorate, a vigorous reaction occured under the
evolution of red-brown gases. No further reaction.
Small chunk amount of NOClO4 maybe 0.2g and a few small mL acetone on a flat surface was a very vigorous reaction, after a small delay a very large
visible volume of dense white gases was evolved (it looked like it was about to ignite, but didn't). The smell was acetic to cyanic, but I didn't
smell more to find out.
0.2g of the NOClO4 in a plastic cap had several drops MEK dumped in at once. Nothing happened until around 2 to 5 sec. after the MEK made contact,
then it started boiling and a flame shot out violently, but the flame did not ignite the mixture. Visible gases given off. Acetone probably reacts
similar in a cap (drenched).
0.1g NOClO4 in a plastic covered metal cap (used to screw closed glass bottles), had maybe about 0.2 to 0.5mL of turpentine dumped in. This changes
color as some red appears. After around 8 to 10 seconds of addition, the mixture began bubbling and boiling a bit, and then after some more seconds
the violence of bubbling increases until the mixture violently burst out into a flame and a sustaining fire formed (had to be extinguished by dumping
water on it, blowing it out didn't work). Eucalyptus oil could yield similar results to turpentine since it also has pinenes and similar molecules.
Urbanski has some good information and section on subjects like this, e.g. organic amines with nitric acid hypergols and rocket fuels. I would highly
recommend this for someone more interested in the subject.
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franklyn
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Related thread
http://www.sciencemadness.org/talk/viewthread.php?tid=6031
Calcium Phosphide ( Ca3P2 ) + H2O -> ( PH3 ) Phosphine
which pyrophorically burns with a bright cherry red flame.
http://www.youtube.com/watch?v=vgh76gPSg3M
Another mixture
http://dl.uncw.edu/digilib/chemistry/general/I-Al%20reaction...
Aluminum or Magnesium powder explodes in contact
with any Halocarbon solution of Iodine
Frozen slurry of Al or Mg with Halocarbon alone at temperatures
of liquid nitrogen -196 °C , explode upon thawing.
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woelen
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A few examples of self-ignition:
Demo 1
- Add a few drops of acetone to some solid NaClO2, such that the material is wetted completely
- Add a few drops of concentrated sulphuric acid and let is soak the material
- Add a small drop of water --> instant explosion with an orange flash of light
Demo 2
- Take a spatula full of powdered Na2O/NaOH mix and put this in a DRY testtube
- Add a few drops of nitromethane --> As soon as the liquid touches the solid a 10 cm long orange flame erupts out of the test tube!
Demo 3
- Take some solid Ca(OCl)2 swimming pool chlorine
- Take some powdered red phosphorus and carefully coarsely mix with a glass rod
- Just wait --> Usually within one minute the mixture ignites with a heavily smoking flame and popping/crackling noises
Demo 4
- Mix 100 mg or so of AgNO3 with an equal amount of magnesium metal (assure that both reagents are perfectly dry)
- Touch the mix with a long wet stick --> A very bright white flash occurs and droplets of molten silver are sprayed around
When doing these demos, please be careful and only use SMALL quantities and always be prepared to cope with (too) early ignition of the mixes. All 4
of these experiments, however, are nice and spectacular demos which can be carried out safely when done carefully.
I tried the NaClO3/conc. HNO3 suggestion further up in the thread, but it did not work for me. No reaction at all, the NaClO3 did not dissolve and the
colorless crystals of NaClO3 became covered with a thin white crust. Apparenty some NaClO3 dissolves, giving a precipitate of NaNO3 which covers the
crystals and prevents any further reaction.
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Formatik
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Quote: Originally posted by franklyn  | Calcium Phosphide ( Ca3P2 ) + H2O -> ( PH3 ) Phosphine
which pyrophorically burns with a bright cherry red flame. |
Departing a little from the subject, USP3944448 describes a thixotropic gel propellant using phosphides and perchloric acid dihydrate (other oxidants
also).
| Quote: Originally posted by woelen | | When doing these demos, please be careful and only use SMALL quantities and always be prepared to cope with (too) early ignition of the mixes. All 4
of these experiments, however, are nice and spectacular demos which can be carried out safely when done carefully. |
That goes without saying for all such mixtures, larger amounts become a strong dangerous fire or explosion hazard.
| Quote: | | I tried the NaClO3/conc. HNO3 suggestion further up in the thread, but it did not work for me. No reaction at all, the NaClO3 did not dissolve and the
colorless crystals of NaClO3 became covered with a thin white crust. Apparenty some NaClO3 dissolves, giving a precipitate of NaNO3 which covers the
crystals and prevents any further reaction. |
Without a fuel, like sugar, I wouldn't expect any spectacular reaction here.
The most spectacular reaction I've seen was by adding a drop conc. aq. HClO4 into a drop of 90 to 99% DMSO (not vice versa so there is some excess of
the latter, the acid must also be as water-free as possible attained by boiling or it won't work), a thump explosion (but no bang) and flash occurs on
the liquid surface, spraying the mixture (Caution! Face shield!). Don't do more than dropwise amounts. DMF was bland, it didn't do anything except it
maybe gave some fumes in the same instance. Adding a drop of acid to a few mL DMSO does the same at the surface turning the liquid deep yellow (I'm
not sure what it is, don't get it on you), some ClO2 is released (ventilation needed). A good demonstration also on why oxidizers and fuels shouldn't
be stored not even anywhere near each other.
Small droplets of NCl3 also detonate violently even under water from olive oil or turpentine. Although easy to make, NCl3 itself has a drawback of
being extremely dangerous. Some description on violence of the reaction described in A compendium of the course of chemical instruction in the in
the Medical department of the university of Pennsylvania:
"The force with which a minute portion of chloride of nitrogen explodes, on contact with oil of turpentine, would hardly be credited by those who have
not witnessed this phenomenon. An open saucer of Canton china was fractured by a globule not larger than a grain of mustard seed."
[Edited on 22-12-2009 by Formatik]
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franklyn
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| Quote: Originally posted by woelen | A few examples of self-ignition:
Demo 2
- Take a spatula full of powdered Na2O/NaOH mix and put this in a DRY testtube
- Add a few drops of nitromethane --> As soon as the liquid touches the solid
. a 10 cm long orange flame erupts out of the test tube! |
Demo 2
Because Nitromethane is acidc , in contact with an Alkali base it will form
the anhydrous Aci-Nitromethanoate salt, a sensitive explosive.
To make Nitronate salts from Nitromethane, non-aqueous solvent such as
absolute alcohol is needed to buffer the reaction from the heat of reaction.
Which is why it instantly conflagrates if only the reactants are present.
From Bretherick's
H2C=N(O)ONa , Sodium nitromethanoate is relatively stable when solvated.
The dry salt is a sensitive and powerful explosive which may be detonated
by warming to 100°C, by a strong blow or contact with traces of water.
The potassium salt is even more sensitive.
| Quote: | Demo 4
- Touch the mix with a long wet stick --> A very bright white flash occurs
. and droplets of molten silver are sprayed around[ |
Demo 4
. . then someone can hang you up on the Christmas Tree. 
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woelen
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| Quote: | | The most spectacular reaction I've seen was by adding a drop conc. aq. HClO4 into a drop of 90 to 99% DMSO (not vice versa so there is some excess of
the latter, the acid must also be as water-free as possible attained by boiling or it won't work) |
I have 200
ml moderately concentrated HClO4 (50% by weight or so). Could this be safely concentrated to the 72% azeotrope by boiling away some water? I never had
the guts to do this, because I have read and heard of explosions while the acid is concentrated and very hot. How safe is it to do this? I would love
to have some HClO4 of high concentration, because so many interesting experiments can be done with that (such as the DMSO experiment, but also making
NOClO4 and IO2ClO4 from NO/NO2 resp. I2O5).
[Edited on 22-12-09 by woelen]
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Formatik
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concentration
| Quote: Originally posted by woelen | | I have 200 ml moderately concentrated HClO4 (50% by weight or so). Could this be safely concentrated to the 72% azeotrope by boiling away some water?
I never had the guts to do this, because I have read and heard of explosions while the acid is concentrated and very hot. How safe is it to do this? I
would love to have some HClO4 of high concentration, because so many interesting experiments can be done with that (such as the DMSO experiment, but
also making NOClO4 and IO2ClO4 from NO/NO2 resp. I2O5). |
Aq. HClO4 is safe to heat as long as you take right precautions, like don't let any organic contaminants fall in, don't overheat it with too strong of
a heat source. Just heat it over a hotplate using merely sufficient heat until you see thick white fumes (Never allow these fumes to absorb onto
paper, cardboard, wood,etc. Don't even heat it near wood in case of a spill. Never heat the acid in a fume hood that it wasn't specifically designed
for!), then heat after that some more, and see for yourself how much heat is needed. Do it under very good ventilation since the fumes are toxic and
can have a choking effect. If done esp. in a beaker, the amount of fumes might seem massive and even after heat is removed it is also an interesting
phenomenon (beats dry ice and food coloring). Try concentration with a small amount like 10mL and then see where you go from there - but beware of
spitting with such amounts - it may be good to use a clamp.
[Edited on 22-12-2009 by Formatik]
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The WiZard is In
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| Quote: Originally posted by Formatik | | Quote: | Originally posted by PHILOU Zrealone
Hi Louis. The glycerin reaction is classical. I think KMnO4 might also ignite some glycol ethers. As a control to the 90%, in the same instance with 35% H2O2 and H2SO4 there was no reaction with acetone, not even gas evolution.
But that is also at small amounts. |
Dr. Ellern in his first book (bet you didn't know there are two!)
Modern Pyrotechnics, 1961. Notes that potassium permanganate
will react not only with glycerin, but also with:
ethylene glycol
erythritol
mannitol
methyglycol
monochlorohydrine
triethanolamine
acetaldehyde
benzaldehyde
Original reference:
H. Rathsburg and H Gawlick. Chem Ztg., 65, 426-7, (1941).
-----------------------------
Organic Chemistry: The practice of transmuting
vile substances into publications.
Anon. |
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