The O ring that can allow mains pressure water to pass to the heating is located on this one.
Near the little x is a small threaded plug with a hole through it. That plug holds in a tiny o ring.
If you drain the boiler and remove the 3 way valve you will be able to see if the o ring is passing by turning on a hot tap.
Oh and by the way also remove the donut washer from the tail peice of the 3 way valve as this plays a part in it as well.
Its the one on the top left of this one
You will probably find that the tail piece needs replacing and the 3 way valve needs refurbing. (requires a special tool to remove the guts of the valve.)