The canned air is actually provided by a liquid that boils at room temperature but is liquid at slightly higher than ambient pressure. This allows them to fit a large volume of gas into a small can without needing to make the can extremely sturdy (or a potential bomb).
As you spray the can the internal pressure drops and the liquid boils, replacing the gas. Transitioning from a liquid to a gas takes energy in the form of heat, called the “latent heat of vaporization”. The result is the cooling of the liquid which in turn cools the can.
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