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Probably the easiest way is to take an NMR and look at the aromatic region (7-8 chemical shift).  p-xylene has 4 equivalent aromatic protons (giving only 1 peak in the 7-8 region), but o-xylene has two pairs of equivalent protons (giving 2 peaks in the 7-8 region).

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Q: How do you differentiate between para-xylene and ortho-xylene?
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