Just before you do- there could be a small leak somewhere in the system, thus when the system cools down air is drawn in to replace the lost water. The only way to be certain is to vent all the rads, tie up the ball cock feed to the expansion tank (the smaller tank) and turn on the boiler for 20 mins or so. If after the system cools down you notice a significant drop of water level in the expansion tank (allowing for the natural contraction of the water through cooling in the system pipework) this could be an indicator of a leak somewhere in the system. Examine all the rad valves, gland packing can fail. If in doubt get an installer to give an opinion.