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The only time (I think) you could see +13 from killing 26 geodudes and leveling up is going from level 99 - level 100
That is, all your EVs, although acquired earlier in the pokemon's life, they do not show up altogether, they are evenly distributed across the levels.
However if your Gyarados does not already have maxed EVs (assuming you used the berries before killing the geodudes) then your Gyarados will indeed have +13 more defense at level 100 than one with no EVs in defense
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Angelic Diablo's PokePet

Slicer the level 46 Scyther!
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