I'm no expert but I am VERY familiar with steam locomoti
Water should not boil in a boiler. The pressure in a boiler prevents boiling, thereby allowing the water to rise in temperature well above 212 degrees. This allows the steam to contain more energy (hotter steam has more energy).
The water WILL boil if there is a drop in pressure, such as a breach in the boiler (a boiler explosion). Also, as you release the pressure, the temperature will drop.
A note on boilers and explosions: There are two main types of boilers, fire tube and water tube. In a water tube boiler, the round case contains the fire and exhaust while the tubes inside contain the water. This type of boiler is pretty common. A fire tube boiler (used on most steam locomotives) contains the water within the round case and the flue pipes contain the hot exhaust gasses and carry them from the firebox at one end to the smoke box at the other.
In a steam locomotive boiler explosion, what usually happens is the water level gets too low in the boiler and goes below the crown sheet (the top of the firebox). With the water no longer on top of the crown sheet cooling it, the crown sheet really heats up and gets soft. The steam pressure (in a locomotive it can be between 150 and 300 psi) is on one side of the softened crown sheet and there is roughly atmospheric pressure below in the firebox. The crown sheet then gets pushed down into the firebox and tears away from the staybolts (which normally hold the crown sheet firmly in place).
First, the crown sheet tears, causing a breach in the boiler. Second, the steam starts escaping into the firebox, where it goes through the flues expanding all the way. Third, the steam starts shooting out of the stack until the stack reaches capacity. Then, the front of the smokebox blows off (this is the round metal plate on the front of the locomotive). The flying smokebox door alone can destroy another locomotive. The escaping and expanding steam will often blow the doors off of the firebox, blowing the fire and scalding steam into the cab of the locomotive, usually killing the engineer and fireman instantly. In severe cases, the boiler can lift off of the locomotive's frame and travel up to a half mile at supersonic speeds. From the moment the crown sheet tears to when the boiler lands can be less than two seconds, all thanks to water under pressure well above 212 degrees flashing instantly to steam upon the release of the pressure.
Less severe boiler failures on locomotives did happen, and people sometime lived, but the scalding caused excruciating pain, long recoveries, etc. etc. If the crew died in the explosion, it was so fast they never would have known what hit them. If they lived, they often had to wait to be pulled from hot wreckage.
Many people have perished in boiler explosions, and it is essential to ALWAYS respect your boiler. Keep it well maintained, insect it regularly, and operate it safely. A boiler is one of the most dangerous (and useful) things man has ever created.
Keep warm, but safely,
Dave