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I suspect overlapping procs are the answer to the first question.
In terms of modeling them: both existing rogue spreadsheets have models for them, and I know the formula has been posted in at least one other thread in these forums - a bit of searching around should turn it up. For rogues the format I find most convenient to deal with is:
p = Proc rate.
n = number of attacks eligible for procs performed each second
d = duration of proc, in seconds.
Then uptime = 1-(1-p)^dn
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