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1. If the rads an HW are being heated the valve has moved to mid-position. The de-energised position is HW only.When my boiler fires up it heats the water and radiators regardless of what is selected. I'm guessing that this means the valve is not moving from the de-energised position?
Its a Honeywell V4073A. The manual/auto lever moves freely both ways and will not latch in the man position.
2. If the lever moves freely, the valve is stuck open. There should be resistance when the lever is move from Auto to Man, and return to Auto when released.
Try this:
Turn the power off at the main switch. (Setting HW and CH to Off at the programmer is not enough)
Check if the lever is stiff or loose.
If loose the valve is stuck open; if stiff, the valve has returned to rest position.
If there is a small bump on the top of the valve, you can remove the actuator (control box). Remove the metal cover then undo two screws (one each side) and remove motor etc. This will expose the valve spindle.
The spindle should be easy to turn by hand - but only about 20 degrees. If it's hard to turn you could try applying some silicon lubricant where the shaft goes though the base plate. (WD40 is not recommended as it can rot the seal.)
If this doesn't work, you will have to replace the whole valve.