your body tells the brain things using nerves. This includes pain.
These nerves use chemical-electric signals.
Electricity can activate a nerve that would not otherwise be active.
So electricity can force all of the nerves in an area to report to the brain, including the ones that report pain. It can also send signals to force muscles to contract in other areas of your body, which also causes pain in that area to be reported to the brain.
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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