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I've read the skill 20 times and done as many internet searches, and I just can't figure out the answer: Does Brimstone Blast deal damage on the initial hit if the opponent fails their reflex save?

Any creature struck by a brimstone blast must succeed on a Reflex save or catch on fire, taking 2d6 points of fire damage per round until it takes a full-round action to extinguish the flames or the duration expires. The fire damage persists for 1 round per five class levels you have. For example, a 15th-level warlock deals 2d6 points of fire damage for 3 rounds after the initial brimstone blast attack.

Does the round you deal damage count as "a round" -- is it saying "yes dummy you do eldritch damage + 2d6 on the round you attack, plus up to 4 additional rounds," or is it saying "melf's acid arrow, bub." The source of my confusion is that the wording that is completely different from how Melf's is worded (which is quite clear on how it works).

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Yes, the fire damage happens immediately, plus up to 4 additional copies on subsequent rounds.

From the SRD:

Catching On Fire

Characters exposed to burning oil, bonfires, and noninstantaneous magic fires might find their clothes, hair, or equipment on fire. Spells with an instantaneous duration don’t normally set a character on fire, since the heat and flame from these come and go in a flash.

Characters at risk of catching fire are allowed a DC 15 Reflex save to avoid this fate. If a character’s clothes or hair catch fire, he takes 1d6 points of damage immediately. In each subsequent round, the burning character must make another Reflex saving throw. Failure means he takes another 1d6 points of damage that round. Success means that the fire has gone out. (That is, once he succeeds on his saving throw, he’s no longer on fire.)

A character on fire may automatically extinguish the flames by jumping into enough water to douse himself. If no body of water is at hand, rolling on the ground or smothering the fire with cloaks or the like permits the character another save with a +4 bonus.

Those unlucky enough to have their clothes or equipment catch fire must make DC 15 Reflex saves for each item. Flammable items that fail take the same amount of damage as the character.

Brimstone Blast changes the amount of damage and removes the extra reflex saves, thus making an action the only way to extinguish it early; but doesn't modify timing.

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