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Your Reading System will display the XHTML files in the order they are listed in the Book Browser in Sigil. Do note that the numbers in the filenames given to the newly created sections after splitting are arbitrary and do not represent the order of the chapters in your book.
You don't need to edit the OPF directly, just open the epub in Sigil and reorder the XHTML files in the Book Browser to the order of your liking (click a file and drag it up and down to a new position).
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