Thermite reaction is also know as a reduction oxidation reaction or redox for short. In order to get a thermite reaction you need a starter of high heat. Typical this is done with a simple magnesium fuse. Once that happens the bond between the iron and oxygen atoms (ie rust) is given enough energy to break. So the oxygen is now free floating but it is not stable on its own. So it reacts with the next most stable thing, aluminum. As the oxygen bonds with the aluminum it releases energy to form that new bond. That energy is enough to break free other oxygen atoms from the rust and cause them to bond with the aluminum. So you have a chain reaction until all the aluminum and iron oxide are reduced.
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