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From the Harry Potter Wiki

Arania Exumai is the incantation of a spell used to blast back acromantulas or other large spiders. If the spell is used on anything but a spider it will produce a large black scorch mark, and thus it is not recommended for use on humans.

Harry pretty much blasted Ron in the face with the spell in the car in the Chamber of Secrets, how was Ron not harmed?

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The spell (used in the movie) was used in the presence of spiders. It's really that simple, I think. I used a Search function on my PDF of the book and it produced "No results." It seems to be an invention of the film and one only used in the presence of spiders.

Why would Harry use it when there were no spiders around?

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I think if it can only be used on arachnids, why would it harm a human if it was aimed at a arachnid? If he said it with no arachnids around and just Ron, I expect it would leave Ron with the black scorch mark. This time it did not because there was an arachnid around.

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The spell cannot harm humans but it can leave black scorch marks on humans or other things that the spell was used on. Spiders are the only thing the spell actually works on

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Welcome to Movies & TV SE. Although this might be the right answer, you might get votes if you provide a link to proof that the answer is right, an explanation of sorts from some website. – New-To-IT Mar 16 '15 at 13:40

This specific spell was only used in the second movie of Harry Potter and was never actually in the books, it was meant to blast back spiders acromantulas specifically.

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