Best Book EVER on Cooking
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On Food and Cooking: The Science and Lore of the Kitchen Hardcover 2004
by Harold McGee (Author)I'm reading it now. It's not a cookbook, but it's about cooking. McGee goes into the chemistry, and stories about what different foods are, why they taste great and why cooking makes things better. Really great book. It probably was meant to be a reference book, but it's also a great cover to cover book.
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I definitely second @Tom-K 's recommendation. I read the book when it first came out and enjoyed it immensely.
It's been a long time...probably worth a re-read!