I guess you're talking about pp blending here. It's a bit like when you mix yourself a G&T by filling the glass half full with ice cubes and tonic water, splashing some gin on top and immediately taking a sip. The gin is sitting on the top with only a little tonic water mixed in, so the sip won't be properly blended. Stir it with a spoon or let it sit long enough for the diffusion to do its job, and it'll be very nice. Except if you decide to wait for the diffusion, all the ice will have melted and your nice G&T will be lukewarm.
The O2 you put on top of the air behaves basically like the gin. And the valve is at the end of the tank, so your gas isn't a mixture from all places inside the tank. At high pressures, the viscosity of gas is rather high, and diffusion is rather slow. But the mixing due to handling of the tank after the fill, and the time for diffusion will do their job, and when you have the same mix everywhere in the tank the gases won't separate again.