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when the engine is "running", the radiator is cooling the coolant. when engine is turned off, the heat built up by the engine will continue to heat the coolant but with the water pump off, there is no cooling interaction with the radiator.
if the system is running at pressure just under the relief point, with little bit of heating, the pressure may be exceeded. my $0.02 worth.
also water is not compressible, it changes stated at the liquid/solid temperature. with coolant added, no idea
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