They only catch fire if prepared in a certain way. You can see the video in the citation url if you’re curious how to prepare it. As for an explanation, the electrolytes in grapes conduct electricity, and the microwave causes the ions in the elctrolytes to move back and forth between the grape halves with the skin acting as a bridge of sorts. The energy from this movement gets dumped onto the skin, which heats up and bursts into flame.
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