Given there's literal seas of hydrocarbons on Titan I wonder if there's a source of oxygen that could be liberated, allowing probes to operate without the need for fuel from Earth?
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Without the need to import fission fuel from Earth, you mean? Where does the energy to liberate that oxygen come from, then?
Depends how tightly bound the oxygen is. If the reaction is exothermic then you capture the liberated oxygen to make far more oxygen in a feedback loop.
I don't get it, are you thinking Titan's just a bomb ready to go off? I'm pretty sure that at least one meteor has hit Titan in the past with the energy of a nuclear weapon, and it's still there. Calculations trying to see if a nuclear bomb would ignite Earth's atmosphere were interesting, but it feels hubristic to think that any nuclear weapon would compare to Chicxulub.
Chemically, things are usually pretty much at equilibrium and if there's a giant energetic cliff, they'll fall off eventually. Nuclear-wise, sure, all the light elements could fuse (hydrogen, helium, carbon, oxygen...) and release energy, but that requires some fairly exotic conditions.
Well, there might be deposits of solid acetylene building up. Those would be explosive.
It would mostly be in the form of CO2, water, with lesser amounts of CO and acetonitrile. I suppose there's some chemical energy in the CN groups (also in acetylenes) but I don't see how that could give free oxygen.
EDIT: acetonitrile doesn't contain oxygen. Duh.