Sciencemadness Discussion Board

Thiocyanat / chlorat

Peter Lustig - 18-9-2017 at 02:23

I found somthing interesting in a book of Richard Escales. There is talk of a mixture of chlorat with thiocyanat which reacts with ammonia and the copper sleeve. I made an experiment: 1 part copperoxid, 2 parts of ammoniathiocyanat, 3 parts of pottassiumchlorat, and mix in littel broth with ammonia solution. After a few houers a blue solid mass is formed, after drying it is sensitive to friction. It gives a nice blue flash... more is not testet yet.

PHILOU Zrealone - 19-9-2017 at 00:49

Nice experiment... but storage may be tricky... so beware.
1°) NH4 thiocyanate is a rich at energy fuel, it contains the NH4 counterpart what is usually uncompatible with chlorate into mixes
2°) There is sulfur bonded into the molecule; if a part of it is oxydized it will set some acidic counterpart what is normally uncompatible with chlorates... but since you have a lot of NH3 free base arround and eventually trapped under a complexated form by the copper as Cu(NH3)4(2+); this may help stabilisation...
3°) CuO, Cu(2+) (eventually Cu(NH3)4(2+)) dont like chlorates... I suspect Cu(2+) to be subject to an oxydoredox with chlorates...
When I used CuCl2, CuCO3 or Cu(OH)Cl as blue flame colourizers of KClO3/C/S/CaCO3 mixes... I got strong corrosion of the iron tin can storage drum and release of Cl2 gas... hence my conclusion...
Also I found very little info about copper chlorate... what may suggest it to be unstable... this is plausible because Cu(2+) is a strong oxydizer (CuCl2 turns easily into CuCl, CuI2 turns spontaneously into CuI, Cu(NO2)2 is unstable, just like Cu(CN)2 ...)

It would be nice that you put pictures of the product and of the testing... blue/green flame are always nice

Edit:
Ah yes not negligible also...
Cu(SCN)2 turns spontaneously into CuSCN and NCS-SCN or NC-S-CN; then upon contact with water HSCN and HCN (highly toxic)

[Edited on 19-9-2017 by PHILOU Zrealone]

Peter Lustig - 21-9-2017 at 01:10

Thank you for your answer. It was stabel for 5 days, I had to test it for a long time, you have quite Copper II thiocyanat is not stabel and NH3 / chlorat is not a good idea. I do not like it being so sensitive. After all, the idea is 100 years old. I think I should not pursue this.

PHILOU Zrealone - 21-9-2017 at 03:49

The basic concept is not bad...

This being mixing KClO3 or other compatible chlorate salts with a compatible unsoluble thiocyanate (or crystallizing dry (without hydrate water) thiocyanate salt... eventually under a complexated NH3 form like Zn(NH3)6(SCN)2 or Fe(NH3)x(SCN)3...

Thus excluding the inherently dangerous Cu(2+), NH4(+)


Edit:
-----
As displayed by Dornier###, mixes of KClO3 with K3Fe(CN)6 and K4Fe(CN)6 (potassium ferro and ferry cyanides) are very potent binary mixes once mixed (grinded) very fine.

Same could be investigated with thiocyanate based complexes

[Edited on 21-9-2017 by PHILOU Zrealone]

Peter Lustig - 21-9-2017 at 04:26

Ineristing ideas. I just found a way to produce Zinkthiocyat Hexamethyltetramin complex Zn (SCN)2 * (Hex)2
What du jou think abaut prussian blu as a componend ?

PHILOU Zrealone - 21-9-2017 at 05:03

Quote: Originally posted by Peter Lustig  
Ineristing ideas. I just found a way to produce Zinkthiocyat Hexamethyltetramin complex Zn (SCN)2 * (Hex)2
What du jou think abaut prussian blu as a componend ?

Yes Prussian blue is an interesting compound...Fex(CN)y
Cyanides are energy rich fuels... such complexes allows for handling cyanides safely because this circumvent the toxicity of the cyanide anion that is trapped Inside the complex and difficult to displace vs other cyanides that react with CO2 from the air and set HCN free...

The Zn(SCN)2(Hex)2 or Zn(SCN)2(NH3)4 (or 6) complexes may be promising as safe binary mixes with KClO3...of course those need to be:
1°) very intimate mixed (ultrafine grinding)
2°) into stoechiometrical amounts in a way to get the best energy output out of the fuel per volume unit.

Edit:
Not to forget the beautiful colorized mixes here...
-Prussian blue has a deep blue colour
-Fe(SCN)3 display a deep red blood
-Other CN or SCN complexes should have entertaining colors
-Not only the complexe color may be at play but also the color when burning...
LiSCN (red),
Ca(SCN)2 (pink-orange),
Sr(SCN)2(red),
Ba(SCN)2 (green)
Too bad the Cu(SCN)2 is unsuitable because the blue color as you mentionned is delightfull into pyrotechnic compositions...

Theorically KClO3/KSCN mix should be detonable


[Edited on 21-9-2017 by PHILOU Zrealone]

dave321 - 21-9-2017 at 11:19

Quote: Originally posted by PHILOU Zrealone  
The basic concept is not bad...

This being mixing KClO3 or other compatible chlorate salts with a compatible unsoluble thiocyanate (or crystallizing dry (without hydrate water) thiocyanate salt... eventually under a complexated NH3 form like Zn(NH3)6(SCN)2 or Fe(NH3)x(SCN)3...

As displayed by Dornier###, mixes of KClO3 with K3Fe(CN)6 and K4Fe(CN)6 (potassium ferro and ferry cyanides) are very potent binary mixes once mixed (grinded) very fine.
[Edited on 21-9-2017 by PHILOU Zrealone]


I believe Pot chlorate and Lead thiocyanate are stable since the mixture was once used in a commercial theatrical bullet hit in the uk. It was also used as a oriming slurry for e-matches.

in a similar way pot chlorate and copper I thiocyanate are also stable .

also, if pot ferricyanide and pot. chlorate are dissolved in minimum water and co precipitated with either ipa or acetone, the dried mixture is extremely fast. CARE ! much more potent than a simple physical mixture.

PHILOU Zrealone - 23-9-2017 at 01:20

Quote: Originally posted by dave321  
Quote: Originally posted by PHILOU Zrealone  
The basic concept is not bad...

This being mixing KClO3 or other compatible chlorate salts with a compatible unsoluble thiocyanate (or crystallizing dry (without hydrate water) thiocyanate salt... eventually under a complexated NH3 form like Zn(NH3)6(SCN)2 or Fe(NH3)x(SCN)3...

As displayed by Dornier###, mixes of KClO3 with K3Fe(CN)6 and K4Fe(CN)6 (potassium ferro and ferry cyanides) are very potent binary mixes once mixed (grinded) very fine.
[Edited on 21-9-2017 by PHILOU Zrealone]


I believe Pot chlorate and Lead thiocyanate are stable since the mixture was once used in a commercial theatrical bullet hit in the uk. It was also used as a oriming slurry for e-matches.

in a similar way pot chlorate and copper I thiocyanate are also stable .

also, if pot ferricyanide and pot. chlorate are dissolved in minimum water and co precipitated with either ipa or acetone, the dried mixture is extremely fast. CARE ! much more potent than a simple physical mixture.

Nice informations Dave321... this validates what I wrote.

For energy output it would be best to make use of bivalent or even trivalent metal thiocyanates in a way to increase the amount of fuel per weight vs the dead weight metal...

I just got the idea that Mg(SCN)2 (MT) and Al(SCN)3 (AT) would probably be very energetic... since the dead weight metal is light vs the fuel counterpart, but they also generates quite some heat as a fuel when producing MgO and Al2O3...

The two products seem stable solids (probably caustic/mordant)(but are they stable towards air/moisture?);
I suspect that they may be an extreme fire hazard... especially if grinded/mixed fine with KClO3...
==> friction sensitivity, risk upon storage
==> If it is the case then NH4ClO4 (AP) may be an alternative to cope with the sensitivity by reducing it a little bit...
The mixes of AP and MT (Magnesium Thiocyanate) or AT (Aluminium Thiocynate) must be very potent for such simple binary pyrotechnic mixes...

[Edited on 23-9-2017 by PHILOU Zrealone]

Peter Lustig - 28-9-2017 at 01:08

I found somthing new: K ( Cu (SCN)3 (HMTA)2 × 2H2O is formed from a solution of KSCN, HMTA and Cu2+. Cu2+ is stabel with thiocyanat in the complex. Can it be that CHP forms NH4 (Cu (ClO4)3 (HMTA)2 ) ? Is Cu (SCN)2 stabel in NH3 complex ?