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Unlike the sugar molecules in liquid syrup, which are free to float around, sugar molecules in the heated, concentrated syrup form these crystals, which line up and arrange themselves in an orderly and repetitive pattern. So as the water evaporates, the sugar molecules bump into one another frequently because there are so many of them, so close together. Occasionally, when they bump into each other, the molecules end up sticking together. This slow process is how the crystal "grows."

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Q: Why do crystals form after you heat syrup but not in unheated syrup?
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