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An ac expansion valve is the part in the ac cycle where the refridgerant goes from a smaller tube to a wider tube. Traveling through this valve causes the refridgerant to get cold similar to cracking the valve on a air tank. When the gasses go from a high pressure to a lower pressure they get cold ( PV = nrT ). The cold refridgerant then goes through an exchager where the blower blows air across to get the cold air you feel when you turn your ac system on.
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I anwered this question Look at post ... "Where is Expansion valve located on 2003 Yukon Denali XL"
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