rubber is an insulator(doesn’t conduct electricity) that also happen to have another desirable property for an insulator: its completely liquid proof, aka Cannot get Wet.
electrocution happens if an open circuit is completed hen you place yourself between the circuit and Ground causing you to close the circuit and create a path for electricity to flow that is less resistant than the current path.
although its no ideal to be touching an exposed circuit(at the very least its gonna hurt like a btch depending on the current) even on the best scenario, having rubber shoes mitigates the risk your making contact with ground, therefore not creating this path..
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