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In short, yes the air does rotate. You're wondering if one molecule of air at the top of the inside of the tire will stay stationary when the tire is moving, basically. Because of the high PSI in a tire, the air molecules are packed together and do not have anywhere to go. When the tire spins, the air doesn't have anywhere else to go, so it starts spinning with the tire.

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Q: Does the air inside a tire rotate with the tire?
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