Is it possible for an iPhone to explode on one's arm?

If it's being used while being charged at the same time?

Yeah, just about any explosive will still make it explode, even while charging.

Possible? Yeah. Probable? Not so much. Rare but does happen. We just don't know why. Best luck.
http://www.siliconbeat.com/2013/08/29/local-man-burned-up-by-apples-response-to-iphone-fire/

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