Your nervous system communicates with tiny electrical impulses. Various receptors that help you register pain, temperature, touch, etc. generate tiny impulses to send that message up to the brain. Your brain makes muscles move by sending them electrical messages.
Getting shocked can screw with all of these things. Depending on how strong it is, it can activate nerves across the burnt surface or cause strong/opposing muscle contractions… both of which hurt. If the electric shock is very intense, the heat from it will start to burn your body: also painful.
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