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Blue and red are two components of light. Blue light has a short wavelength, while the wavelength of red is long. The shorter the wavelength, the stronger the light scattered. (Blue light is strongly scattered.)
During the day, the sky looks blue because of this strong scattering. At dawn and dusk, light passes through the atmosphere for a longer period, which scatters blue light waves. Red and orange, with their longer wavelengths, dominate because they scatter less, which is why the sky looks red early in the day and when the sun is setting.
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