So here is what the stone does.
This stone absorbs your soul as the magic jar spell immediately prior to your death. You can't transfer your soul from the ioun stone receptacle to another creature's body, and are, for all intents and purposes, dead. While your soul is in the ioun stone, you can sense any life forces within 120 feet as though you were placed in a magic jar. At any point within 12 hours of your soul's transfer into the pale orange rhombus ioun stone, you can return to your body as long as it is within 120 feet of the ioun stone. Upon returning to your body, you are unconscious and dying with a number of negative hit points equal to your Constitution score minus 1. If you fail to stabilize and aren't healed after 1 turn, you die and your soul is not absorbed by the ioun stone. Your soul can be absorbed into a pale orange rhombus ioun stone only once per 24-hour period.
My question is. A player of mine has 3 of these. Only 1 is bounded. Would the bounded one be activated first or would he be able to choose which was to be activated first? He is arguing that he would be able to use one of the unbounded ones first then be able to come back to his body and if he dies again he could then go back into the bounded one. I would think that the bounded stone would go first but I would like to know what everyone thinks.
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A) Your player has an insane amount of money. I'm assuming this is pure theorycraft.
B) When you say "bounded" I assume you mean it's implanted using the rules from Seeker of Secrets? The answer is that you are the GM so you get to decide. I would rule the same as you. It's not a conscious act on the part of the PC, it is the stone that grabs the soul, so it makes sense that it would be the one he took the time to bond to and then implant into himself.
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An ioun stone does nothing unless it has been activated - either orbiting his head, implanted, in a wayfinder on his person, or using another game ability that applies the stone's enchantment.
However:
Your soul can be absorbed into a pale orange rhombus [sic] ioun stone only once per 24-hour period.
The additional stones are pale orange rhomboid ioun stones, so the character's soul's ability to enter one is limited by this note, regardless that they are not the same ioun stone that activated first.
An ability that allowed him to stabilise automatically would reduce his danger.