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Popcorn Balls

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Your question is a good one. I've often wondered the same thing myself, so I did a little research and found this explanation on a very reliable candy-making website:

In a candy syrup, the sucrose molecules of sugar react with water in the presence of an acid to form an invert sugar. This means that as boiling continues, a portion of the sugar separates into its constituent parts—glucose and fructose. Adding cream of tartar and a dash of vinegar to a toffee recipe helps bring about this change. The presence of invert sugar is important because it influences the amount of crystal formation as well as the size of the crystals that form as candy hardens.

That may make you want to return to your high school Chemistry class. Also, that particular response was to a question about Toffee, but I found other references to the acidity of vinegar helping the sugar boil properly and form the correct crystalline structure.

Making candy can be tricky. Maybe the addition of vinegar and/or cream of tartar provides just a little extra insurance that your efforts will be successful.

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