Sciencemadness Discussion Board - Anhydrous perchloric acid ?

Anhydrous perchloric acid ?

DubaiAmateurRocketry - 29-6-2013 at 00:20

How do i make anhydrous perchloric acid ?

I have ammonium, lithium perchlorate. I will get Sodium perchlorate soon.

And i guess NaClO4 + HCl = HClO4 + NaCl ?

does NH4ClO4 + HCl = HClO4 + NH4Cl ?

Does LiClO4 + HCl = HClO4 + LiCl ?

ok so, I know i cant find pure HCl since it boils at -80 degree, I am able to make anhydrous H2SO4.

by getting liquid SO3 distilated from decomposition of a sulfate salt + H2O 1:1 by mole.

Does 2 NaClO4 + H2SO4 = 2 HClO4 + Na2SO4 ?

or 2 NH4ClO4 + H2SO4 = 2 HClO4 + (NH4)2SO4 ?

So are those steps possible to get HClO4 ? i will have a fume hood very soon so ill do all those inside them, and i will be protected by mask glove glass and stuffs, so dont worry

[Edited on 29-6-2013 by DubaiAmateurRocketry]

hyfalcon - 29-6-2013 at 01:35

You don't want to make anhydrous perchloric acid. Anything over 70-72% will blow up in your face.

Finnnicus - 29-6-2013 at 05:59

You did start a thread about Ti(ClO4)4. Later on, you can find alot of warnings about perchloric acid. Follow these.

As for the chemistry-
Making HClO4 from the salts is done with sulfuric acid. See this kewl as thread for the SM reference. (Thanks Woelen!)
Bubbling SO3 through the solution will help if your acid is not truly anhydrous.

Please correct me!

Endimion17 - 29-6-2013 at 06:18

Anhydrous perchlorid acid? ROFL, don't even try it.

DubaiAmateurRocketry - 29-6-2013 at 06:20

Quote: Originally posted by Finnnicus

You did start a thread about Ti(ClO4)4. Later on, you can find alot of warnings about perchloric acid. Follow these.

As for the chemistry-
Making HClO4 from the salts is done with sulfuric acid. See this kewl as thread for the SM reference. (Thanks Woelen!)
Bubbling SO3 through the solution will help if your acid is not truly anhydrous.

Please correct me!

I put water into SO3, not SO3 into water. I can get SO3 gas from decomposing something and i can condense it easily.

I need anhydrous perchloric acid, to make titanium IV perchlorate, i can obtain Titanium IV chloride very cheap and easily so i really really want to make it

[Edited on 29-6-2013 by DubaiAmateurRocketry]

sargent1015 - 29-6-2013 at 07:19

Are you just like, not reading the posts?

Anhydrous HClO₄ is dangerous!

Endimion17 - 29-6-2013 at 07:22

Quote: Originally posted by DubaiAmateurRocketry

I put water into SO3, not SO3 into water. I can get SO3 gas from decomposing something and i can condense it easily.

I need anhydrous perchloric acid, to make titanium IV perchlorate, i can obtain Titanium IV chloride very cheap and easily so i really really want to make it

[Edited on 29-6-2013 by DubaiAmateurRocketry]

Say again, how come you're still alive?

Dude, anhydrous HClO4 is prone to detonation. Do you have any idea what you're trying to accomplish here? I guess you don't.

And what's this shit about mixing sulphur(IV) oxide with water? It detonates upon contact with it. That's why it's mixed with concentrated sulphuric acid to make oleum, which is then dilluted.

BromicAcid - 29-6-2013 at 07:50

You can make it from nitric acid and ammonium perchlorate. You will find references if you look long enough. You basically mix the reagents and continue to boil them while replenishing the nitric acid. In this way the concentrated perchloric acid formed oxidizes the NH4+ to various nitrogen oxides. Although the gas generation is profoundly unsafe it still might be better than distillation. Of course at best you will get azeotropic acid out of that. From there you need phosphorous pentoxide (IIRC).

Of note, you mention hydrochloric acid boiling at -80C. Surely you meant hydrogen chloride. Hydrogen chloride does not become hydrochloric acid until it is dissolved in water which tames it considerably and substantially increases the boiling point.

You can also try to dissolve sodium perchlorate in hydrochloric acid then gas out the sodium chloride with gaseous hydrogen chloride.

Edit: In a moment of insanity I thought that the first reaction mentioned used hydrochloric acid instead of nitric acid as it is usually done.

[Edited on 6/29/2013 by BromicAcid]

woelen - 29-6-2013 at 10:39

As mentioned here above, making anhydrous perchloric acid, just for the goal of making rocket fuel is insane. Anhydrous perchloric acid is extremely dangerous and if you go on, mixing KClO4, NaClO4 or whatever xxxClO4, then you soon will loose some limbs or more! Do not do that! Anhydrous HClO4 cannot be kept around for more than a few weeks. When stored in the cold (e.g. a fridge) it usually explodes after appr. one month of storage. If your bottle is not perfectly clean or is not stored in a cool place, then explosion occurs earlier.

It also can explode on contact with dust from the air, stuff like plastic, wood, rubber, grease. Contact of anhydrous HClO4 with the reducing agent DubaiAmateurRocketry also leads to immediate explosion (and yes, I mean this, this is not a joke!).

Fantasma4500 - 29-6-2013 at 11:02

this might be something you want to take a look at
http://www.youtube.com/watch?v=y_lgZVTyLzA
the author im sure will not mind
it was explained that HClO3 when it goes past around 30% conc. it goes into HClO4, and this was ANHYDROUS HClO4

the explosion was created by adding paper
now think for a second how this would turn out with magnesium

DubaiAmateurRocketry - 29-6-2013 at 11:04

Ok i know its dangerous, I am making around 20 grams only, and inside a fume hood.

and im adding titanium IV perchlorate at negative 10 degree. so its ok. Im making T IV P

[Edited on 29-6-2013 by DubaiAmateurRocketry]

hyfalcon - 29-6-2013 at 11:24

What's the name of the local newspaper so when you stop posting we can check of whether you managed to launch yourself into orbit without a vehicle.

Guys, just back off and let Darwin do his job. If he's hell bent on committing suicide then we've warned him of the danger.

[Edited on 29-6-2013 by hyfalcon]

[Edited on 29-6-2013 by hyfalcon]

Endimion17 - 29-6-2013 at 11:53

Next project, nitrogen trichloride. Ten grams, at most.

AndersHoveland - 29-6-2013 at 12:11

LiClO4 would make a slightly better rocket fuel oxidizer than NH4ClO4. The reason it is not used is because lithium salts are actually fairly expensive, particularly in bulk. Anhydrous HClO4 cannot be used in rockets. It is too unstable and would detonate.

kristofvagyok - 29-6-2013 at 13:23

Quote: Originally posted by AndersHoveland

The reason it is not used is because lithium salts are actually fairly expensive, particularly in bulk.

Lithium salts are not used as rocket fuels, because they are highly hygroscopic, they do not have a really high price...

Anyone interested in buying 150kg of lithium-chloride? We got a barrel of it and it is useless for us... It hardened a bit, because of a little water absorbed from the air, but it's still good as a table, or as a water absorber, just place it in the corner and it will leave no humidity in the room in no time.

phlogiston - 29-6-2013 at 16:15

Quote: Originally posted by DubaiAmateurRocketry

Ok i know its dangerous, I am making around 20 grams only, and inside a fume hood.

and im adding titanium IV perchlorate at negative 10 degree. so its ok. Im making T IV P

[Edited on 29-6-2013 by DubaiAmateurRocketry]

I'll drive on the highway 200 km/hr wrong way, but I'll only do it for half an hour, and I'll use a safety belt. so its ok.

I can only hope that you have no access to the required chemicals untill you learned a bit more. Otherwise, rest in peace my friend.

Endimion17 - 30-6-2013 at 03:02

You mean - rest in pieces?

Perhaps he's just trolling us?

testimento - 30-6-2013 at 12:58

I was going to make ammonium perchlorate by first making a pile of sodium perchlorate and then solve it in water, bubble hcl to remove chlorates and then bubble hcl to get perchloric acid solution and remove salts and then bubble ammonia gas to get ammonium perchlorate. Highest concentration Im gonna use perchloric acid is 70% azeotrope, should this be considered very dangerous?

AndersHoveland - 30-6-2013 at 13:17

70% perchloric acid is more dilute than you may think. This concentration is by weight, not by molar proportions. The hydrogen have barely any mass, while the chlorine atom has twice the mass of an oxygen. 70% perchloric acid would have lower performance than NH4ClO4.

madscientist - 30-6-2013 at 18:16

Quote:

Ok i know its dangerous, I am making around 20 grams only, and inside a fume hood.

20 grams is enough to kill you, and the fume hood will offer you no protection - the sash will turn into shrapnel and only make your wounds more gruesome. Be sure you warn your labmates, so the innocent may live to see another day.

woelen - 30-6-2013 at 22:50

With highly explosive materials even 1 gram may seriously hurt you. Commercial firework crackers may not have more than 50 mg of flash powder in them and if you keep such a thing in your hand while it explodes, then it feels like someone hits you with a hammer on the fingers. Imagine what happens if 1 gram of an even more powerful compound detonates! With 20 grams detonating in the fume hood in front of you, there will be a highly gory view for the others who have to clean up the mess.

madscientist - 1-7-2013 at 02:18

Woelen speaks the truth.

With quantities like 20g, I wouldn't even trust a blast shield to provide adequate protection. Detonations have a remarkable ability to disintegrate nearly everything, and to turn that which does not into projectiles traveling at hundreds or thousands of meters per second.

Quote: Originally posted by AndersHoveland

LiClO4 would make a slightly better rocket fuel oxidizer than NH4ClO4. The reason it is not used is because lithium salts are actually fairly expensive, particularly in bulk. Anhydrous HClO4 cannot be used in rockets. It is too unstable and would detonate.

I suppose this is also why Timothy McVeigh chose to use NH4NO3 instead of LiNO3?

DubaiAmateurRocketry - 2-7-2013 at 10:49

Well i have a fume hood, ok i got it i know its very dangerous in first place, well any easier way to Ti(ClO4)4 ?

I am guessing LiClO4 adding in TiCl ? will that work ? or LiClO4 dissolved in a xxxx solvent that will not react with TiCl ?

Or NaClO4 ?

Random - 2-7-2013 at 10:54

Quote: Originally posted by DubaiAmateurRocketry

The following is an extract from the C.R.C. Handbook of Chemical Safety *
“Considerable interest has been taken in the explosive hazards to be encountered in the use of
perchloric acid since a mixture of perchloric acid and acetic acid exploded in a Los Angeles
factory in 1947, killing 15, injuring 400, and causing $2 million damage. On a smaller scale,
Robinson reported a detonation of 3g 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 benc
h top and chipped walls over 15 feet away.
Fortunately, this happened in an empty laboratory
."

[Edited on 2-7-2013 by Random]

DubaiAmateurRocketry - 2-7-2013 at 10:55

So, can someone help me predict if there is ion exchange between

TiCl4 and , LiClO4, NaClO4, or NH4ClO4 ? Doing it in ethanol since it can dissolve most of the above.

If there is, i can make titanium IV perchlorate... my dream salt !

[Edited on 2-7-2013 by DubaiAmateurRocketry]

woelen - 2-7-2013 at 22:46

TiCl4 almost certainly will react with ethanol. I would not be surprised if this make ethyl chloride and hydrous TiO2, or ethyl chloride and some basic titanium chloride. TiCl4 will be a chlorinating agent, not as strong as PCl3 and co., but it most likely will be strong enough to attack simple low carbon alcohols.

kristofvagyok - 3-7-2013 at 01:48

Quote: Originally posted by woelen

TiCl4 almost certainly will react with ethanol.

Reaction of TiCl4 and ethanol will yield HCl and titanium-ethoxide (Ti(OEt)4).

TiO2 could be also produced by this method, only thing what should be present is a little water, since the Ti-alkoxydes hydrolyze easily. EtCl will not be produced.

But I would recommend to use another solvent, what is aprotic, maybe toluene. Since it dissolves Li-perchlorate and TiCl4 also.

DubaiAmateurRocketry - 3-7-2013 at 10:01

Quote: Originally posted by kristofvagyok

Quote: Originally posted by woelen

TiCl4 almost certainly will react with ethanol.

Toluene seems convienience, you sure it dont react right ? because i have little knowledge in titanium compounds, and compounds that react with water.

kristofvagyok - 3-7-2013 at 10:20

Quote: Originally posted by DubaiAmateurRocketry

because i have little knowledge in titanium compounds, and compounds that react with water.

In this case I would like to kindly suggest to look up the scientific literature what is about these problems.

ScienceSquirrel - 5-7-2013 at 16:27

Titanium IV perchlorate can be made in various ways eg mixing anhydrous perchloric acid with titanium tetrachloride.
To me this sounds like one of the ultimate nasty reactions with lots of going wrong potential.
I remember my youth when the boss suggested we made a range of metal chlorides by heating metal oxides in a tube furnace in a stream of carbon tetrachloride vapour, the other product was phosgene.
A half hearted start was made on the project but despite encouragement it gradually ran in to the sand and was finally abandoned as cowardice or good sense, depending on your point of view, and more interesting and safer synthetic targets took over as objectives for the group.