As the sun sets the sun is further away from us, therefore the light has further to travel. Suspended in the sky are tiny particles that scatter the light that leaves the sun, when the sun is higher up the blue is the colour which we see first because red has a longer wavelength and therefore takes longer to get to our eyes. When the sun is setting the particle density is much high, so blue and the other colours get scattered before they have chance to travel to us.
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