Make sure the drive is formatted Mac OS Extended (Journaled)
1. Quit iPhoto
2. Copy the iPhoto Library from your Pictures Folder to the External Disk.
3. Hold down the option (or alt) key while launching iPhoto. From the resulting menu select 'Choose Library' and navigate to the new location. From that point on this will be the default location of your library.
4. Test the library and when you're sure all is well, trash the one on your internal HD to free up space.