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I am assuming that when you say you "Reader Library" that you mean Sony's Reader for PC, and when you say you double click on a book you are doing that in Windows Explorer?
If so, you probably just need to change the file association for Reader for PC. Many ways to skin that cat in Windows 8, including those ways in earlier Windows versions. In case not familiar with those, probably the quickest is:
On the Start Page (with all the tiles), start typing Control Panel and on the left hand side of the screen options will pop up, one of which will be Control Panel. Click it to start Control Panel and find "Default Programs" and open it. Select "Set your default programs" and scroll down to Reader for PC and select whichever of the two options at the bottom of the page that you want and follow your nose.
If for some reason Reader for PC does not show up in the above, then as before after opening "Default Programs" select "Associate a file type or protocol with a program" instead and scroll down to select each of the file extensions you want Reader to open by default (.epub, etc.), click "change program..." and select Reader for PC.
If you didn't mean Sony's Reader for PC then just do the same but for whatever program it is that you are using.
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