I am not sure what is the off-voltage and on-voltage. Can you explain please?Actually the voltage when the MOSFET is off is basically a constant, since although the inductor current is changing, the voltage does not as long as it is pulling current through the diode and charging the -5V output capacitor.
Then to get the average voltage you just take the off-voltage and the on-voltage and use the duty-cycle to calculate the average.
Mod: Link to earlier thread.
https://forum.allaboutcircuits.com/threads/buck-boost-converter-mosfet-voltage.161847/post-1476959
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