Cooling systems are pressurised to increase the boiling point of the coolant, so the temperature could easily exceed 100 degrees centigrade.
IIRC a radiator cap incorporating a 13 PSI pressure relief valve will not allow the system to boil until the temperature reaches about 125 C.
That's what makes releasing the radiator cap on a hot engine dangerous - once the pressure is released, the coolant, which may be above it's boiling point at atmospheric pressure instantly boils, blowing hot coolant out over anything (and anyone) in it's way.