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For more on marking an answer as the "Best Answer", please visit our FAQ.Coffee, as an example, burns mouths as well as when spilled on ones arm, but the mouth has several protective mechanisms that your arm does not.
"When you drink hot coffee, you do it very slowly, cooling it down before it can burn your mouth", says James Nachbar, MD, FACS, Plastic Surgeon, Phoenix, Arizona. "The mucosa [a membrane lining] in the mouth has a very rapid blood supply," he says "and blood flowing through the blood vessels in the lining of the mouth carries away some of the heat."
Saliva also cools the hot coffee.
Furthermore the lips and tongue are so sensitive they force you to take in coffee only as fast as the mouth can cool it, says Dr. Nachbar. Arms, being less sensitive, can suffer a burn before you realize the danger. Finally, clothes hold the hot spill against your skin, which increases the risk of a serious burn.
(With thanks to Wonder Quest)...