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Conductivity is related to the size of an atom - the bigger the atomic radius, the easier it is to pick electrons off the edge of the atom.

Silver has a larger atomic radius (160 pm) than gold (135 pm), despite the fact that gold has more electrons that silver.

One caveat though is that in the presence of oxygen silver will corrode and thus become a worse conductor than gold, Gold on the other hand (except under certain extreme conditions) does not corrode, that's why electrical contacts are often gold tipped, to prevent signal degradation do to corrosion.

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