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Go to Control Panel, then System. In the Hardware tab, there's a button for the Device Manager. In the Device Manager, there should be a line something like "IDE ATA/ATAPI-controllers, with "Primary IDE Channel" and "Secondary IDE Channel" under it (when you click on the + sign). Now for both of those, you can doubleclick on them and it should give a dialog which contains an "Advanced Settings" tab, so choose that. You'll get an overview for device 0 and device 1, these are Master and Slave on that particular channel. The easiest way to look for the optical drives is to check the Current Transfer Rate. The optical drives are almost always Ultra DMA Mode 2 or PIO while the hard drives are Ultra DMA Mode 5 or 6.
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