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The reason an AC system works more efficiently while the vehicle is in motion is because a change of state of the refrigerant and a heat exchange occurs when air flows through the condenser fins. The better air flow you have, the more effective this is. A moving vehicle produces much more air flow than a sitting vehicle. However, even at idle, the air should still be cool. If you're getting warm air when the vehicle isn't in motion, then you probably have an insufficient amount of refrigerant in your system.

If you're asking why it doesn't work when the motor isn'trunning, it's because the AC system - which runs off a compressor which runs off the motor via a belt - isn't in operation - only the blower motor is. Without cool refrigerant cycling through the evaporator to be blown into the passenger compartment, the blower motor will blow the ambient air at whatever temperature it is into the passenger compartment, instead.

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Q: Why will your car not blow cold air with air conditioner on while sitting still?
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