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Rainbows are formed when light is reflected and refracted around the inside of water droplets. When the droplets get to a certain size, the light is reflected an additional time, creating a secondary rainbow.

The reason you see both a primary and a secondary rainbow (or even higher orders of rainbow) is that the water droplets which are reflecting the light have different sizes. Some of them are large enough to fit the extra reflection inside them, whereas some are not.

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