Each color of a character's name in the VIP list has a different meaning:
Once a player logs into their account and selects a character to play that character moves from the offline state to the pending state and will just see the splash screen of their client. At least on the Flash Client that character's name on a VIP list or chat channel will appear orange. Once the character enters the game their status changes to the online state.The purpose of the pending state is to add some safeguards. Before the pending state was added in Updates/9.8 a character could be considered online before the screen loaded and so they could be attacked and not know it. Now they are only online when the screen fully loads. Also when a character dies they now enter the pending state, instead of offline, and if the reenter the game their channel content will be preserved from before the death, they will not lose their party status, and if the character contributed to killing a creature they will be counted among the killers.
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