You can not de-authorize a single machine without physical access to it. That is obviously since otherwise Apple couldn't enforce the maximum of 5 machines authorized at the same time (I leave it as an exercise to you why that is so).
Once you have used up all your 5 authorizations, Apple allows you to de-authorize them all at the same time (without physical access). You do this within your iTunes account screen in the iTS. You can do this only once a year though.