It's just a naming convention. The rules of nomenclature were somewhat arbitrary at first. Then the need of standardization became apparent, and so formal naming rules came into play (sort of).
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Octane < Carbon tetrachloride < Methanol
alpha naphthol with CCl4(carbon tetrachloride) gives blue colour whereas beta naphthol with CCl4 gives no colour. that is the distinction test between alpha and beta naphthol.
109.5 degrees
Zero
5.25 is lower, so it would go first.