When the boiler cools, it sucks in air.
Total gas pressure is the sum of the pressure of all the gasses.
wiki Dalton's LawWhen the boiler heats, the pressure is held at ~1 bar, which is the sum of the air pressure and the steam pressure.
When you bleed the boiler, you remove [some of] the air.
Because the pressure is lower, the boiler heats to ~1bar again.
Once all the air is removed, the water is at ~1bar steam temp and the pressure is maintained.
It's SOP to bleed a boiler a cupla times before using the steam.