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Solid phosphoric acid is not anhydrous and contains water molecules. The water molecules can dissociate to produce hydrogen ions, which are then available to catalyze reactions. When solid phosphoric acid is used as a catalyst, it is typically heated to a temperature at which water molecules can dissociate. The alkyl hydrogen phosphate product is a result of the reaction of the phosphoric acid with the alcohol. If the phosphoric acid was anhydrous, it would not be able to dissociate and would not be able to catalyze the reaction.