4s 5000mAH vs 5s 5000mAH runtime??

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The 5s 5000 would be like most like a 4s 6000mah for run time if you gear for the exact same speed (say 40mph) as long as the additional voltage didn't put your motors RPM's out of the sweet zone. If you deviate in speed like the others stated it would throw this off and you can end up with the some gain in run time or a loss in run time depending on your setups with each.