Why does wearing many layers of cotton clothes keep you warmer in winter than wearing one thick sweater?

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Layering clothing ensures that there is an insulating space between each of the layers, and your body heat is retained within the layers. A single sweater may be warmer than any one individual layer, but cannot retain your body's heat in the same manner. That said, wearing a wool knit fishermen's sweater as your top or "second to top" layer is an excellent idea when it is quite chilly (wool both retains heat and repels water better than artificial yarns, due to its lanolin content, but a waterproof jacket should be worn over it in the case of rain).
The other real advantage to layering is that temperatures are rarely stable throughout the day: if you wear layers when you dress on a chilly morning, you can remove some when it gets warmer during the day. If you're only wearing one thick sweater and remove it, you might be arrested.
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