There is something odd here, and that relates to the yellow wire which you say shows 240v when it is disconnected from the other wiring. I would not expect to see any voltage there. Bear with me on this as I'm not too good explaining things in writing, but I will have a go.
In installations like yours, the yellow wire would normally be used as a 'switched live' to the boiler, and indeed, based on that assumption, your photographs show exactly what I would expect to see, as follows:
1. The yellow wire is connected to the orange wire from the motorised valve. The orange wire is made live by the valve when it winds to the H position and provides the 'on' signal to the boiler via the yellow wire when heating only is required.
2. The yellow wire would also be connected to the cylinder thermostat, so that when hot water was required the cylinder thermostat can also start the boiler.
This is what I see in your photos and is exactly what I would expect.
So far so good. However, in your case:
Yellow wire is temporarily isolated......With CH only selected, the pump comes on, the boiler fires and the radiators are getting warm.
The boiler should not be running with its switched live disconnected, but it would appear that it is. Are you really sure that the boiler actually fired up, or was the pump just circulating already hot water it contained? [The pump would still run if it was still connected to the motorised valves orange wire.]
This raises the following questions.
1. Why is the boiler running when the switched live supply appears to be disconnected?
2. Where is the 240v on the yellow coming from?
3. Is the yellow actually being used as the boilers switched live? if not what is?
When you get chance, can you confirm that my last sketch shows the wires from terminal to terminal as they are actually connected, and can you find the other end of the yellow wire and tell us what it is connected to or post a photograph please.
Apart from you changing the motorised valve innards when the problem occurred, has anything else been changed?