Nevermind, just figured it out, I think :?
The last tank was an old one and the heater exchanger entered and left the tank on opposite sides, I believe (and have yet to check) that the exchanger on the new one enters and leaves the cylinder on the same side ... I've plumbed it wrong ... I'm...
I have just managed to double check the cylinder type (physical check) and can see the heat exchanger inside ... it IS the right tank ... thankfully!
I have also plumbed it as is was before, i.e. same as the old one ... so what's going on, somebody else has suggested that it could be to do...
The main cold water tank is situated slightly higher (although this is as it has been since before I started doing any work on the system).
I've noticed that the vent stops when I turn the valve from the cold water tank off. Also, I've found that turning the pump on stops the expansion tank...
I have just replaced my immersion tank (indirect from coal fired back boiler) and having completed that (finally!) I turned all the water back on and have now found that the vent into the expansion tank won't stop running, the expansion tank has been overflowing out the overflow and I'm left...