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From the Minecraft Wiki:
"A rail in the "on" state will accelerate a minecart if any of the following is true:
1. The minecart is already moving, in which case the cart is accelerated in the direction of motion
2. The minecart is stationary, but one end of the powered rail is up against a solid block. In this case, the cart is accelerated in the direction that is not blocked.
3. The minecart is stationary, but the powered rail is on a slope. The instant the powered rail is activated, the brake is released and the cart will start moving down due to gravity. As the cart is now moving, rule (1) applies and the cart is accelerated in that direction."
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