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methylated spirit is in fact methanol added to ethanol (usually 10% methanol is used). The liquid evaporates which means that the liquid converts to a gaseous state. This process requires energy which it extracts from your body in the form of heat. This same process cools you down when you sweat. The reason that spirits feel colder than say room temperature water is that the boiling point of alcohol is much lower than water(about 78 degrees C for ethanol and 100 degrees C for water). This means that at room temperature the partial pressure of ethanol is higher which means more of it is evaporating from your skin than water, requiring more energy(which makes your hand feel cold).

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