True ^^ either way will work. Just don't waste 10 gallons of water for nothing.
Measuring this by the concentration of the sugar in wort (hydrometer or refractometer) at the beginning & end of the boil is an exact way to know your boiloff rate. You'd have to accurately know your pre-boil volume.
I'd do this with check with making a beer and estimating about 1 gal/hr boiloff for a rolling boil for planning purposes.
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