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If you mean in a car engine, it's because an explosion (even a controlled one of the gasoline/petrol being ignited by a spark plug) creates a spherical force. So, the cylindrical piston is the same shape as the explosion, and gets the most efficient pressure distribution. A rectangular piston would get force in the middle, but not the edges, and it would take more force to do the same job. Also, the rectangular piston would wear down faster because of the uneven force being applied.

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Q: Why cant we use a rectangular piston where in the edges are chamfered?
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