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Let's say I have a large quantity of rust and want to extract the oxygen from it in a way that allows me to collect the oxygen in a container.

What chemical process can I use to do this and what equipment does it require?

It's preferable if the process is doable at home so I can demonstrate the process but it's not mandatory.

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Good question; unfortunately, no good answers. The problem is that oxygen, pure oxygen, doesn't like to exist as such; it will form a diatom like many gases, but it's very electronegative, and so it will prefer to get the extra electrons from something more willing to donate them, like the iron. This is why "oxidation" has that name; until fluorine was isolated in the mid-1800s, oxygen was the strongest known electron acceptor ("oxidizer"). It's easier to run a reaction that gives the oxygen something else to oxidize, producing the raw metal, than to get the iron to complex with something else and release the oxygen. In at least one circumstance, this is very good for humans and other aerobic organisms; oxygen complexes with the iron in your hemoglobin for transport to your cells. In most other circumstances, we could do without this behavior.

Rust is insoluble in water but will dissolve in strong acids. It will react with hydrochloric acid to form iron chloride and water (sometimes producing hydrogen gas if there isn't enough oxygen to go around). The easiest "household" method to obtain oxygen from iron oxide, therefore, is to dissolve the rust in muriatic acid forming iron chloride and water, neutralize any remaining HCl by adding lye to form sodium (and/or potassium) chloride and water, distill the water from the chloride salts by boiling and then cooling the vapor, then electrolyze the water with a battery to produce oxygen and hydrogen. That's cheating, though. First, water's water, and you're adding far more to the party with the acid and base solutions than you would ever get from the rust. Second, muriatic acid and lye, while available in relatively pure form for pool maintenance and for soapmaking respectively, are not exactly everyday household chemicals in those forms (both are components of other household chemicals, such as drain cleaner and lime scale remover, but are somewhat difficult to isolate from them).

Theoretically, if you heat the rust enough, the components will dissociate and you'll be left with pure iron and oxygen. Unfortunately, even with carbon in the mix (producing elemental iron metal and carbon dioxide, which is the reaction behind iron ore refinement and recycling), the minimum temperature required for this reaction to become favorable is 842K = 569*C ~= 1056.2*F. I can't find data on iron-oxygen bond enthalpy or entropy, which is needed to calculate the spontaneous decomposition temperature of the compound, but logic states it's much higher than with added carbon, because you're not getting any energy release by forming the carbon-oxygen bond, so every Joule of energy needed to break the iron-oxygen bonds has to come from outside the material. Theoretically it would cost you about 2.5kWh/kg of heat added to the iron; in practice the amount of heat you'd have to generate (and lose to various inefficiencies) to get the metal that hot is beyond any household device's capabilities, unless your hobby happens to be glassblowing.

The "thermite reaction" between iron oxides and aluminum under heat is another well-known method of separating the iron and oxygen. The rust and aluminum powder, given some initiating heat, will exchange the oxygen to form alumina (Al2O3) and pure iron, and enough heat to keep the reaction going (with plenty to spare; a thermite reaction is too bright to watch without a welder's mask and in fact is used in some situations to weld iron). Two problems with this; first, it's illegal in the US to make thermite without BATFE approval, and second, the reason it works at all is because aluminum oxide is ridiculously stable, more so than iron oxide, and so it takes even more energy to reduce the oxide back down to the raw metal (about 8.2 kWh/kg for aluminum, theoretical, versus 2.25kWh/kg for iron). This is evidenced by the highly exothermic nature of the thermite reaction itself; if creating aluminum oxide produces far more than enough heat to smelt the iron to get the oxygen, think of how much would be needed to go the other way.

Pretty much the only direct route to releasing oxygen gas from rust without a blast furnace is to introduce an even more powerful oxidizer. There are very few known to modern science, and none of them are "household chemicals" to say the least. The easiest to work with would be elemental fluorine gas, and the experienced chemists in the crowd will know that for the extremely relative statement that it is. Fluorine is the most electronegative element in the known universe, and so pretty much any substance that isn't already highly fluorinated (like some polymers, such as Teflon) will react pretty vigorously with it. That includes the water, proteins, enzymes and other compounds in your own body; a fluorine gas leak is a "drop everything and run" type of emergency. As used on rust, the fluorine will simply barge in and displace the oxygen from the rust to form a white to pale green iron fluoride, liberating the oxygen as a gas. You then have to separate the oxygen from the excess fluorine, and one of the standard ways in industry to catch excess fluorine is to pass the exhaust gas over or through a powdered sodium oxide filter, which will form sodium fluoride and liberate more oxygen in a very similar reaction as you got with the iron. Sodium oxide isn't a pleasant chemical to work with either; add water (such as by breathing in any loose powder) and it forms the strong base sodium hydroxide, which eats flesh about as efficiently as anything else you could think of.

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  • $\begingroup$ You can also go via the same process used for aluminium: electrolytic smelting, either directly (probably), or using a solvent. Not exactly doable at home, though! $\endgroup$ – Aesin May 17 '13 at 20:53
  • $\begingroup$ A long read but a fantastic answer, seems it wouldn't be too easy to do even given the right industrial equipment! $\endgroup$ – RhysW May 17 '13 at 21:41
  • $\begingroup$ @Aesin - Electrolytic smelting is pretty much the same basic iron-for-carbon redox as in a blast furnace, but using electrical arc plasma to generate the necessary heat in a more localized fashion. And no, not exactly the type of thing you could do at home unless you leveraged the main 200A trunk line into a monster DC converter. $\endgroup$ – KeithS Jul 29 '13 at 21:38

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