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An adventure pours a vial of acid on an enemy combatant. I assume the enemy will try to avoid this.

How can this be handled with the rules of the game? How does this change if the acid vial is thrown?

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This is written in the Player's Handbook on page 148:

Acid. As an action, you can splash the contents of the vial onto a creature within 5 feet of you or throw the vial up to 20 feet, shattering it on impact. In either case, make a ranged attack against a creature or object, treating the acid as an improvised weapon. On a hit, the target takes 2d6 acid damage.

Remember that a ranged attack in melee range gives you disadvantage, so that covers the part where the enemy is trying to avoid the attack.

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    \$\begingroup\$ I wouldn't have said it's the "disadvantage while within 5'" rule that models the enemy trying to avoid it, it's the fact that the enemy has an AC. \$\endgroup\$ – nitsua60 Aug 2 '17 at 14:59
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    \$\begingroup\$ I agree with nitsua and to elaborate, the explanation for the "disadvantage while within 5 feet" rule is that it's much harder to aim a ranged weapon because the person within 5 feet of you is actively trying to impede your aim. In the context of a vial of acid, this could be them trying to grab your arm to stop you from throwing it. For a bow it could be them pushing the bow aside. \$\endgroup\$ – zach Aug 2 '17 at 16:02

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