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I agree with gammac. If the cap isn't holding the correct pressure, it will open to the vent plus it's the cheapest thing to try. A system needs to be pressurized to raise the boiling point of water. I forgot the ratio but for every pound of pressure your cap is rated, it raises the boiling point so many degrees. If you didn't have a cap on, you would overheat quickly. Most shops should have a cap tester.
It shouldn't be the thermostat. If the stat was stuck closed, the engine would overheat and coolant not going to the rad. If the stat was stuck open, the engine would run cold.
uncleterry,
I believe there is a test for the coolant if there is combustion gases present. You may also see bubbles if you can look into the rad opening while it's running. Also pull the plugs, if one of the plugs is bright white, it may be burning coolant from a bad head gasket. There may not be coolant in the oil depending on where the gasket may be leaking. A cylinder base gasket would be more likely to get coolant in oil.
Run the engine to operating temp with the rad cap off. That should bleed off any air pockets in the system.
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