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Sounds like you may have a bad rear thermostatic valve in the rear AC unit. One way to check is to get some AC manifold gauges, start the car, turn on just the front AC, check the gauges, and have someone turn on the rear AC. While this is happening, see if there is any change in the pressure readings, if there is no change, then you have bad valve, If there is a change (and I mean 10 - 20 psi) then you system may be undercharged, which means you need to locate and repair the leak and recharge the system.

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