OK, so 103kWh for 1 hour is running at 103kW... (or 138HP).
and your water flow prediction is 123HP at 72% pump flow. - suggesting 90% efficiency if the burner is at max, not "72%"... (I don't believe you have 125% efficiency, but suspect the pump is not 100% efficient?
Piston pumps, in the hydraulics world, generally have an efficiency in the low 90's.
Being and axial pump, 89%-91% would probably be an okay assumption.
When mathing out efficiency for a *quality* water axial pump I would typically use 90%.
1714 psi/gpm(constant for 100% efficient pump) *.9 = 1542psi/gpm per hp(745.7W)
So using 1542 as a constant, with a known pressure and wattage, should give the theoretical flow which can be cross checked against the pumps displacement at x RPM.
If the unloader is being used in throttling, then the above goes out the window unless you know if the back pressure is cracking the unload piston open a little or if the unloader is very sensitive and is simply open or closed.
I assume here that the unloader is fully closed as the back pressure would be very low unless there is a nozzle or other restriction inline to provide sensing back pressure.
For what it's worth, that axial pump has such a tiny heat sinking area that there should be no valve between it and the steam tubes, pwm (as you are using) is superior for flow control because back pressure opening the unloader is going to be stupidly hard on the suction and discharge valves due to water heating from the recycled unloader and the resulting cavitation of the heated water. (Around 53° most pumps start to die iirc). The water in an axial pump is also removing the heat from the wobble plate and pistons so you really want good flow.
You definitely don't want to be throttling with just a needle valve or similar inline restriction valve.
However:
Throttling with a restriction type valve can be done if you add an inline unloader down-stream from the pump and run the extra unloaders output through a long hose or into a reservoir to allow cooling. Note the down-stream unloader will need to be set much lower then the pump unloader.
While I am rambling:
Other factors that affect axial water pump longevity is that they typically (I've never seen one that does not) need a minimal inlet pressure and are unsuitable for suction from a reservoir because of cavitation, they really suck at pulling in water.
So if you are going to measure output volume, don't attach the pump suction side to a reservoir without an inline booster pump (something variable/dynamic like a centrifugalpump). Flow would be best measured at the output with the pump attached to your existent pressurized water supply ie. Your home.
Sorry if this is all known stuff.
Back to my bridge...