even at max skill it fails quite a bit. i lack experience how it was on live though though i think the 100% succes rate was only acheived with AA later on.
further i read the following:
Quote:
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The higher skill you have applying the poison, the faster you will be done applying it. At the start you will need 7 seconds to put a poison on your dagger, later it is rumored to be significantly less, but I still cannot accomplish that.
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source:
http://kikyara.tripod.com/basics.html
can anyone who played a rogue on live confirm / deny? here it doesn't seem to make a difference to how long it takes to apply.