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You can think of the expansion valve as a small hole. On one side of the hole is high-pressure ammonia liquid. On the other side of the hole is a low-pressure area (because the compressor is sucking gas out of that side).
By the way, if you have ever turned your car off on a hot summer day when you have had the air conditioner running, you may have heard a hissing noise under the hood. That noise is the sound of high-pressure liquid refrigerant flowing through the expansion valve.
Pure ammonia gas is highly toxic to people and would pose a threat if the refrigerator were to leak, so all home refrigerators don't use pure ammonia. You may have heard of refrigerants know as CFCs (chlorofluorocarbons), originally developed by Du Pont in the 1930s as a non-toxic replacement for ammonia. CFC-12 (dichlorodifluoromethane) has about the same boiling point as ammonia. However, CFC-12 is not toxic to humans, so it is safe to use in your kitchen. Many large industrial refrigerators still use ammonia.
In the 1970s, it was discovered that the CFCs then in use are harmful to the ozone layer, so as of the 1990s, all new refrigerators and air conditioners use refrigerants that are less harmful to the ozone layer.
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