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The frost stat (which measures air temperature) and pipe stat (measures water temp and fitted to return pipe) should be wired in series. The boiler lights when the air temperature drops below the frost stat setting (5-10C). The pipe stat turns the boiler off when the water returning to the boiler reaches the set temperature (25C).Checked and found both are operating as frost stats. If either are switched on the boiler comes on but not the pump! All seems a bit odd as the two stats are literally a foot apart. So much for my theory that the pipe stat was an overtemp device.
If there is no pipe stat, the boiler temperature will rise until the boiler stat operates - may be 80C. This would heat the house unnecessarily and be wasteful.