What is an outdoor air thermostat?
This is an enhancement or alternative to the primary control. Some boilers have a remote sensor that checks the outdoor air temperature. Again, there are a number of ways that this can be arranged, but some simply have the boiler water kept hot (within a range) when the outdoor temperature drops below a set point (e.g., 60F).
The outdoor-air temperature sensor or outdoor-air thermostat arrangement recognizes the inefficiency of keeping a large boiler hot when there may not be a call for heat for some time. When the outdoor temperatures are high, the boiler is allowed to get cold. As the outdoor temperature drops, the boiler heats up, anticipating a demand for heat from a thermostat.
These systems are used more in commercial than residential construction, although you may find them in large homes.
It's possible to use an outdoor-air temperature sensor to automatically increase the temperature of the boiler water as the outdoor temperature falls. The colder it gets outside, the hotter the water in the boiler is maintained. This ensures that heat will be quickly available when called for by the thermostat.
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