Sciencemadness Discussion Board - Iron Perchlorate

Iron Perchlorate

mabuse_ - 22-2-2012 at 06:08

Hi there,

has anyone here ever attempted to synthesize this compound?
Megalomia suggests perchloric acid & iron sulfate.
Perchloric acid is of course unavailable to me.

But I might get or make barium perchlorate, since BaSO4 is water unsoluble I might just filter it off....?

Any experience?

Ral123 - 22-2-2012 at 08:25

What's so cool about it? Id get a fluoride if I were you

AndersHoveland - 22-2-2012 at 18:32

Not sure if ferrous perchlorate would explode if heated, but the decomposition would probably be:

4 Fe(ClO4)2 --> 2 FeOCl + 2 FeCl3 + 15 O2

FeOCl is iron(III) oxychloride

[Edited on 23-2-2012 by AndersHoveland]

mabuse_ - 23-2-2012 at 00:45

I don't care if it's explosive as long as I can handle small amounts safely.
I just want to try the 5-NTZ iron compounds mentioned in the green primaries documents.

caterpillar - 24-2-2012 at 01:42

My Dad made experiments on Fe2+ -> Fe3+ oxidization, and he uses Fe(ClO4)2 for that purpose (I do not remember why this particular compound was used). He made it by dissolving iron powder in HClO4, I do not know its concentration- surely not 100%. Once reaction vessel exploded during this process. But this salt is highly soluble and its crystals content plenty of water. I do not think that this salt is particularly dangerous due to large amout of aforementioned water, that it contents- to get dry salt will be real headache.

AndersHoveland - 24-2-2012 at 07:01

Quote: Originally posted by caterpillar

made experiments on Fe2+ -> Fe3+ oxidization, and he uses Fe(ClO4)2 for that purpose (I do not remember why this particular compound was used).

Perhaps because the perchlorate anion is typically inert to reduction at normal temperatures. In contrast, the reaction of nitric acid with iron, even dilute, causes the reduction of some of the nitrate anions.

caterpillar - 24-2-2012 at 14:06

May be, but why not FeSO4? As I remember, he made experiments at Ph 6-7 approximatelly, using ZnO as a buffer to keep acidicy at the same level.

dann2 - 31-3-2012 at 14:25

What is below is from here:
www.dtic.mil/dtic/tr/fulltext/u2/273203.pdf

_____________________________________________

PREPARATION OF REAGENT - IRON (111) PERCHLORATE
1. To a warm solution of dilute perchloric acid (75 ml HCI04 + 40 ml H20 ) in a 600 ml
beaker, gradually add 50 grams of ferrous perchlorate while stirring the solution on a
hot plate. Add more distilled water if necessary to dissolve the crystals.

* 2. Cover the beaker with a ribbed watch glass and evaporate the solution to strong
* fumes. Continue fuming until traces of iron (Ill) perchlorate begin to crystallize from the
solution.

3. Remove the beaker from the hot plate, cool, and filter through a dry, clean, sintered
glass filtering crucible. Any trace of moisture will transform the white (tinted purple)
crystals to a yellow color.

4. Wash the salt with about 100 ml of perchloric acid which has previously been fumed.

5. Recrystallize the salt in a manner similar to the above procedure using the same
amount of perchloric acid mixture. For the second filtration, the crucible should be tared.

6. Dissolve 60 grams of the moist recrystallized salt (dried by vacuum) in a mixture of
270 ml HCIO4 plus 230 ml H 0. Any amount of reagent can be prepared providing the
4 2
same proportions are adhered to.

Dann2

AJKOER - 26-4-2012 at 06:41

Here is a released US government study titled "Research on the Exploration of Methods to Produce Chlorates and Perchlorates by Means Other Than Electrolytic", indicating the possibility of producing a perchloric starting with a Chlorate salt, Ozone and a strong mineral acid (HClO4, or 65% H2SO4, or HNO3):

Reactions cited by the authors:

1 3 NaCl03 + 2 HCl04—>3 NaC104 + 2 Cl02 + H2O
2. 2 ClO2 + 2 O3 + H2O --> Cl2O7 + H2O + 02—> 2 HCl04 + 3 02
3. NaCl03 + O3 --> NaCl04 + 02

I was thinking that an Ozone generator with time might work here as the O3 source. The chlorate can be produced via a disproportionation reaction on a select hypochlorite.

Link:
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=AD0017221

AndersHoveland - 28-4-2012 at 14:17

Quote: Originally posted by AJKOER

2. 2 ClO2 + 2 O3 + H2O --> Cl2O7 + H2O + O2—> 2 HClO4 + 3 O2

I do not think this reaction is entirely accurate.
While O3 can oxidise Cl2 to Cl2O6, I do not think the Cl2O6 can be oxidised any further, at least not to Cl2O7. But in the presence of water, ClO2 certainly can be oxidised to perchloric acid, even very concentrated HClO4. I just do not think Cl2O7 is an actual intermediate in this reaction.

[Edited on 28-4-2012 by AndersHoveland]

Mumbles - 4-5-2012 at 22:17

Iron (II) Halides are produced from a methanol suspension of iron metal in methanol with the added aqueous acid. (see Inorg. Syn. 14 pp 101). This is followed by dehydration of the hexamethanol salt by heating under vacuum. Is there any reason this may not work for preparation of less coordinating salts like perchlorate or BF4 or something? Granted this may not get you to Iron (III) if that is your goal.

AndersHoveland - 4-5-2012 at 22:28

I would suspect iron(II) perchlorate may not be the most stable substance. I found this:

Quote:

Ferrous nitrate, Fe(NO3)2, is prepared by dissolving iron in cold dilute nitric acid. But a considerable amount of ammonium nitrate is also formed in the solution, according to the reaction:-

4 Fe + 10 HN03 --> 4 Fe(N03)2 + NH4NO3 + 3 H20.

This solution is very unstable and decomposes when heated even slightly, forming basic ferric nitrate and liberating nitric oxide.

Ferrous nitrate crystallises from solution after some time in four-sided bevelled prisms, having a very faint greenish colour and sharp taste, [and is] deliquescent

However, perchlorate ions tend to more chemically inert than nitrate ions. The reaction of 65% concentrated perchloric acid with iron would not reduce any of the perchlorate ions, only hydrogen gas would be given off.

[Edited on 5-5-2012 by AndersHoveland]

AndersHoveland - 21-6-2013 at 22:05

Quote: Originally posted by caterpillar

My dad was a chemist. He studied reactions like Fe++ -> Fe+++, Cu+ -> Cu++ and so on. Once a girl in his lab put some iron powder into HClO4, wanting to prepare Fe(ClO4)2. I do not know, which concentration this acid has- surely not above 70%, but explosion occurred just when this girl arrived to my dad to report that all is correct and reaction is going well...

Perchloric acid (assuming it is not >72% conc.) just reacts with iron like any other normal non-oxidizing acid, releasing hydrogen.

However, Fe(ClO4)2 is an explosive, as much energy left to be released when Fe²⁺ gets oxidized to Fe³⁺. Perhaps the girl was heating the solution over a hot plate. Even when not in solid form, some of these types of solutions can still exothermically decompose violently. This is the case for solutions of tin(II) nitrate.

Quote:

Solutions of Sn(NO3)2 are reasonably stable. However, attempting to evaporate the solutions to dryness results in decomposition, which can in some instances be violent. The decomposition products are mainly SnO2, nitrous oxide, and hydroxylamine, with other oxides of nitrogen also produced.

[Edited on 22-6-2013 by AndersHoveland]

DubaiAmateurRocketry - 21-6-2013 at 23:25

How to make Iron III perchlorate then ?

AndersHoveland - 21-6-2013 at 23:36

Iron(III) perchlorate would be a Lewis Acid, and would probably form adducts with many solvents.
While the hydrate exists, it might be rather difficult to prepare anhydrous Fe(ClO4)3, as the oxyperchlorate OFeClO4 would instead tend to form.

You might see the thread "Titanium IV Perchlorate Ti(ClO4)4".

[Edited on 22-6-2013 by AndersHoveland]

madscientist - 30-6-2013 at 18:55

Quote:

Compare vacuum distillation of DMSO over Mg(NO3)2 vs. Mg(ClO4

2. Have your next of kin report the results of your generalization.

[Edited on 1-7-2013 by madscientist]

AndersHoveland - 8-7-2013 at 23:35

sensitivity, of course, is not the same thing as chemical reactivity. Many perchlorate compounds tend to be fairly sensitive to detonation when organic groups are an integral part of their molecular structure. I would also suspect, under these anhydrous conditions, that the magnesium ion tends to act as a lewis acid, decreasing the perchlorate ion's stability

Quote: Originally posted by madscientist

Have your next of kin report the results of your generalization.

seems like you are the one making generalizations here. Dissolving metals in hot 60% perchloric acid is actually a non-issue, besides from the obvious dangers of a concentrated boiling hot acid. The one unusual exception being if the metal being dissolved is bismuth.

The hazards of perchlorates/perchloric acid cannot easily be generalized. In many situations they are surprisingly tame, in other situations there are hazards that can be very difficult to foresee.

Could iron(III) perchlorate potentially form dangerously explosive adducts with a range of organic compounds? Yes, it could certainly be possible. particularly with DMSO, it may be able to displace the water of hydration

[Edited on 9-7-2013 by AndersHoveland]

Fantasma4500 - 9-7-2013 at 01:45

i think you might want something else but H2SO4 in the end, as you cant really boil it away that easily
gives off SO3 also in the process, think twice about that
perhaps use Fe2O3 Fe3O4 or FeCO3 or even Fe(OH)2
also BaSO4 is very very very fine particles
i dont see how you could seperate that easily
perhaps nanoglass filter with vacuum would do the job
a thing that would be more interesting would be lead perchlorate
lead chlorite Pb(ClO2)2 decomposes pretty rapidly
axt has a video on it on youtube

madscientist - 9-7-2013 at 04:34

AndersHoveland, I am not sure how you came to the conclusion that a single statement pointing out a specific case where you are gravely wrong could be considered a generalization. Perhaps you do not understand what generalizing is?

Quote:

I would also suspect, under these anhydrous conditions, that the magnesium ion tends to act as a lewis acid, decreasing the perchlorate ion's stability

Your usual speculative guessing. Anders, try acting like a scientist - that generally

involves keeping your mouth shut.

Quote:

Could iron(III) perchlorate potentially form dangerously explosive adducts with a range of organic compounds? Yes, it could certainly be possible.

No shit it can.