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Not all hydrates can be done by simply heating them for some reasons. Some hydrates like AlCl3 decomposes when heated. Upon heating AlCl3-nH2O, it decomposes to HCl and Al(OH)3.
Some hydrates are very strong meaning, they are stable to heat. Consequently, heating them can drive off some water molecules, BUT not all.
Some hydrates can be heated but not for long because formation of other substance may proceed.
Some hydrates have low boiling points thus as it is being heated, water molecules can come out as well as the compound itself.
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