I don't think it's a sign of hunger, but I have a private theory that sometimes snakes yawn when a smell interests them, say when they're in a new setup or scenting food; they have that Jacobsen's organ in the roof of their mouth that enhances their sense of smell, a bit like a cat's 'Phlemen reaction' - have you ever seen a cat sniff something interesting and then adopt a rather dopey dropped-jaw expression? They're getting the most out of that scent.
Snakes will often yawn after a feed, it's said to re-align their jaw (not surprised!)
And sometimes they'll yawn, I think, just because they want to ...