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White is defined by the color of the sun. Since we evolved within its light we of course see the distribution of wavelengths that make it down to Earth's surface as white. Even if the sun was always orange, we would see that as white instead.
Why do we see it as yellow, then?
During the day it's white, but it's also overhead and blindingly bright so we don't spend much time looking at it. As it gets closer to the horizon Rayleigh scattering begins filtering out the bluer light and the sun becomes yellow, then orange, then red. It also gets closer to our eyeline and becomes mildly safer to look at so we look at it a lot more. This in turn leads us to believe it's always yellow