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What causes electrocution
When performing service on appliance or equipment, always turn electricity OFF.

Never assume power is OFF.

Safety switch located within sight of water heater, air conditioner, or equipment such as table saw can offer protection against electrocution. It is easy to determine if electricity if OFF, and electricity cannot be accidently turned ON at breaker.

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Electrocution: People get electrocuted, because they become the pathway for electricity to reach earth. Although it is not known exactly what electricity is, we can say that it has to do with charged electrons seeking, or moving, to equalize the charge with other electrons.
All matter is made from atoms. Under typical conditions, each atom has negatively charged electrons in orbit around a nucleus that contains positively-charged protons. The charge between the proton and orbiting electrons is balanced, and there is an attracting force in the universe that tries to keep the charge balanced.
The universe wants to equalize the charge.

Because electrons are small and lightweight, many things cause them to jump free from orbit, including heat. Conductive materials, such as copper and aluminum (electric wire is made from copper and aluminum), give up atoms more readily than insulating materials like rubber or air.
Once free, the negatively charged electrons are attracted to any matter that carries a different, or unequal charge.
When it happens, the electrons jump from atom to atom to atom etc, creating what we describe as electricity.

For example, a static shock from rubbing feet across a carpet and touching a doorknob is caused by unequal charge.
The electrons that came loose by friction (heat) of feet on carpet are equalizing with the charge on the doorknob. Of course the number of electrons is small so you are not harmed. All matter is conductive. If you touch the wood door instead of metal door knob, the electrons will also discharge, but the movement of electrons in an insulating material like wood is slower. The metal doorknob is a conductive material, so all the electrons discharge at once.

The shock from a live electric wire is much larger than a static charge from carpet.
The power plant generator rotates a magnet past coils of wire, and the process of magnetic induction causes electrons on the wire to start jumping from atom to atom and flow down the wire.
Read about electric generation
Electricity is 'highly charged' because it carries enormous numbers of charged electrons. The earth will always have a different charge than electrons on a live electric wire.
As a result, electrons on the wire will follow any pathway to earth in an effort to equalize the charge. Except the generator keeps pumping out charged electrons and if you become the pathway for all those electrons, it will kill you as the electrons burn though the body. That's one basis for electrocution, but doesn't cover all possible hazards.

The ground wire helps reduce the risk of electrocution by offering a resistance-free path for electrons to reach earth.
A ground wire is required for each electrical installation. The ground wire is connected to all other ground wires to form an array of grounding that is connected to a ground rod that is driven into the soil to proper depth to meet local soil conditions.
A properly installed ground wire offers no resistance to the flow of electrons.

What is resistance? Imagine that charged electrons are like marbles, and resistance is a hill that surrounds the marbles and stops them from rolling away.
If there is no resistance, the marbles can freely roll away.  Electrons will 'roll away' like marbles when they are attracted by an unequal charge.
If there is resistance, or a hill surrounding the marbles, then the marbles can only roll away if they get piled up so high and the charge becomes so strong that they spill over the top and overcome the resistance.
A properly installed ground wire should have no resistance, while a person's body offers a fair amount of resistance, and so the ground wire becomes the easiest pathway for electrons to follow, thus helping to prevent electrocution in some instances.

However, if electrons are running wildly into the ground wire, the Hot wire that supplies the source of electrons becomes overheated by the massive number of electrons pouring down the wire. The circuit breaker detects the heat, trips, and cuts off the flow of electrons.
A problem arises because circuit breakers are 'slow acting,' and will not trip immediately. This means the ground wire and breaker cannot protect someone exposed to live electricity while standing in water or on bare soil or touching a grounded object such as clothes dryer or hull of a ship.

For safety, make sure to avoid becoming the pathway for electrons by following basic electrical safety practices, testing if power is off, not wandering around at night after a storm blows down power lines, and installing ground fault interrupter (GFCI) on any vulnerable circuit. Circuits that need GFCI include bathroom, kitchen, laundry room, and outdoor outlets, switches and equipment.

GFCI will instantly react to the rush of electrons just as they start to flow on the wire, and cut off the circuit before the person gets killed.

How GFCI works:
Each single phase circuit requires two wires. The number of electrons flowing on each wire is identical because of how electric power is generated. The GFCI is connected to both wires, monitoring the number of electrons on each wire. If one wire suddenly has more electrons, then it means electricity is flowing to ground somewhere in the circuit, and the GFCI instantly trips off the circuit, stopping the flow of electrons. So if you are standing outside in a puddle of water and holding an extension cord that is frayed and causes live electricity to enter your body, the GFCI detect the flow of electrons so quickly, that you will not get electrocuted. Use double-insulated tools outdoors, make sure cords are in good condition, and always connect to GFCI-protected circuit.

Ground wires are permanent and do not need periodic checking at a home or business unless a direct hit by lightning melts the wire. GFCI and circuit breakers can go bad and usually fail in OFF position, but should be checked periodically for heat and malfunction.
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Other causes of electrocution
-Lightning. During a storm, the electromagnetic nature of the universe causes unequal charges to gather in the clouds.
The updraft of hot air into cold clouds causes friction between air molecules that frees negatively charged electrons from positively charged protons, similar to how rubbing socks across a carpet creates a static charge. 

Because air is a good insulator, it stops the charges from equalizing. As a result, pockets of charged electrons and protons gather in different areas of the clouds. The charge in one pocket will be different from the charge in another pocket. The charge is also different than the charge on the earth below. The storm now carries a huge number of unequal charges that want to equalize, except for the resistance of air. 

Air has high resistance. That's why high voltage power lines are suspended above the ground. The higher the voltage, the higher the wires have to be. The power lines carry electrons that will jump to earth if a pathway exists. The air helps stop the electrons on the wire from equalizing with earth.

Inside a storm cloud, the electrons are not free to equalize because air offers resistance. The charged electrons must build up in massive numbers before they overcome the resistance. When the charge becomes large enough, the electrons will flash across the sky in a bolt of lightning, just like a static spark when you touch a doorknob. The lightning will equalize the charge.
The bolt of lightning will continue until the resistance of air exceeds the remaining charge. 
If electrons build up again, another bolt of lightning will occur from the same area. 

If a person is struck by lightning, the charge can burn through the body, tearing out muscles, shorting the brain, heart and nervous system. Outcomes vary. Lightning can hit nearby, and jump from object to object finding any pathway to discharge, including someone standing nearby.

-Electric chair: Basically the human is connected to 2 Hot wires, one at the top and one at the bottom of the body. Each wire carries electrons with exactly opposite charge of the other wire. When the switch is pulled, the electrons burn through the body, similar to a light bulb, except unlike the light bulb, the human has more resistance which requires considerably more electricity. 
The final outcome, if done correctly, is resolved within minutes. If done incorrectly, the human may survive somewhat. 
In any case, there is a reason why a hood is placed over the person's head, as electrocution radically distorts facial muscles, causing a spectacle that might give doubts about the humanity of such actions.

-Stealing copper wire: Copper theft is a profession that attracts the less affluent from society, yielding a lottery-like chance of electrocution, prosecution, or if lucky, a few dollars toward the day's human needs. If done correctly, the work offers exciting opportunities without benefits. Done incorrectly then negative outcomes range from serious burn to getting carbonized into a charcoal lump as the body becomes the pathway for electrons on the wire to equalize with earth until power company switches off the breaker. 

Electricity is a trap. Once the electrons start to flow through a body, the muscles contract, making it impossible to release oneself from the hazard. Once grabbed, a person is stuck until the electricity burns through the body. Anyone grabbing the affected person will also become stuck unless a friend knocks them loose with a 2x4 or pulls them off using a belt or dry towel. 
I do not recommend copper theft, and suggest careful study beforehand, but acknowledge that on-the-job training is cheaper than paying for trade school or college.
Safety 
More people are killed by 120 volt that all other voltages. Do not touch a person being electrocuted, knock em loose with a non-conductive 2x4. Do not apply water to electrical burn. Get help immediately.
People making the error of stealing copper wire and transformer oil at substations are frequently burned into carbon. The suffering is quick once high voltage strikes a human body, except for folks who witnessed the event. 

I don't mean to sound indifferent, more than advising caution. I was working on live 120 volt in customer's attic. Sweated shirt and leaning into metal AC duct, the next thing I remember was coming back to consciousness while crawling toward the attic stairway. I was unhurt because the contact was brief, but SWORE never to work on live power again. Good idea.
 

Turn power off. Always stand on dry insulated surface such as boards when working with electricity. 
Turn off breaker, but do not assume power is off. Test with non-contact voltage tester. 
When testing live power, tape tester leads to wood sticks to keep hands away from power. Paint sticks and masking tape work fine. 
Do not lean over and put head into live circuit. Step back and then pick up tools. 
Stay off aluminum ladder. Use approved fiberglass ladder, or safest plan: hire licensed electrician and go out and buy a newspaper.
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