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During the middle of the day, the sun is for the most part above our heads. This means the sunlight goes right through the Earth's atmosphere. During sunrise and sunset, the sun is hitting the Earth and the Earth's atmosphere at an angle. When the light hits the atmosphere the light is broken up, appearing in the sky as many different colors. The similar thing happens when you shine a ray of light into a prism, it comes out as many different colors.

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