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If your car is tuned for 91 octane and you put in 100 octane, you will see no difference in performance. If you tune it to take advantage of the 100 octane, you will.
The only exception to this is when you have a computer that will "learn" the conditions that you run your car under. It compensates for "bad" gas and "good" gas. An example would be an BMW M5. Another example is a knock sensor setup.
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