Disclaimer: I do not have a Ph.D in chemistry, physics, or anything of the like.
With that said - volatile substances are only volatile when there is potential for a reaction to occur. Once a reaction has occured, or the potential otherwise removed, the substances are no longer volatile and are quite stable.
This is the reason Chlorine can be a poison gas used in warfare (unreacted, volatile elemental state) and food staple in the human diet (in the reacted, molecular form of Sodium Chloride). There really isn't a reason why ships wouldn't be coated in a layer of pre-reacted tritanium or something considerably less reactive than elemental tritanium to prevent explosions while in dock. Of course, ship damage would have to covered up before you dock, but given that nanites seem to be common as dirt in the EVE universe, it wouldn't surprise me if processes similar to armor- or hull-repair processes could be used to "paper over" the damage until a more permanent fix can be arranged.