The air pressure in the expansion vessel is very inportant, thats what make it do it's job (or not), with your system (water) pressure at zero and the PRV open* attach a tyre foot pump to the schroder valveon the expansion vessel and pressurise it to around 1 bar. * Some pressure releif valves (PRV) can be set in the open position by rotating the red top a little, others have to be held open to release the system pressure so you might need some help.
After pumping to vessel to 1 bar, close the PRV and re-pressirise the system to around 1 - 1.2 bars, if every thing is ok there should be very little movement of the pressure as the system goes from cold to hot certainly nothing like the rise you have mentioned in your earlier post, that is why the expansion vessel is fitted.
Re your leak, you didn't say if you have a hot water cylinder fitted or is it a combi type boiler? If you hava a cylinder it can be difficult to tell if the indirect coil which is pressurised is leaking into the DHW which is at a lower pressure s it is fed by the tank in the roof space, you could: mark the water level in the cold water tank in the loft ( do this with a peice of wire hooked over the edge of the tank and cut off so it just touches the water surface, you now mustleave it for 24 hours or so making sure you dont use any hot tap or any other low pressure colds taps that are fed by that tank. Best to do this with the boiler turned off, when you see your system pressure has dropped to zero then check the water level in the tank, if the level has risen (the end of the wire is under water) and you are sure the ball valve is not letting by, I would then say the coil has failed, there are other ways of proving but the the method above works for me. Hope this helps (I know it might be a bit difficult to understand)
Martin