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Hitting with the shin is always going to do more damage just because your tibia (shin bone) is dense, long, and "sharp." The extra power generated by the 8 inches or so longer moment arm (physics talk) is countered by the fact that the tendons in the foot and the slight seperation of the bones in the foot absorb more of the power. Long story short, both can knock you out, but the shin is more likely to do so
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