Refrigerant

A refrigerant is a substance or mixture, usually a fluid, used in a heat pump and refrigeration cycle. In most cycles it undergoes phase transitions from a liquid to a gas and back again. Many working fluids have been used for such purposes. Fluorocarbons, especially chlorofluorocarbons, became commonplace in the 20th century, but they are being phased out because of their ozone depletion effects. Other common refrigerants used in various applications are ammonia, sulfur dioxide, and non-halogenated hydrocarbons such as propane.

The ideal refrigerant would have favorable thermodynamic properties, be noncorrosive to mechanical components, and be safe, including free from toxicity and flammability. It would not cause ozone depletion or climate change. Since different fluids have the desired traits in different degree, choice is a matter of trade-off.

The desired thermodynamic properties are a boiling point somewhat below the target temperature, a high heat of vaporization, a moderate density in liquid form, a relatively high density in gaseous form, and a high critical temperature. Since boiling point and gas density are affected by pressure, refrigerants may be made more suitable for a particular application by choice of operating pressures.

Chlorodifluoromethane

Chlorodifluoromethane or difluoromonochloromethane is a hydrochlorofluorocarbon (HCFC). This colorless gas is better known as HCFC-22, or R-22. It is commonly used as a propellant and refrigerant. These applications are being phased out in developed countries due to the compound's ozone depletion potential (ODP) and high global warming potential (GWP), although global use of R-22 continues to increase because of high demand in developing countries. R-22 is a versatile intermediate in industrial organofluorine chemistry, e.g. as a precursor to tetrafluoroethylene. R-22 cylinders are colored light green.

Production and current applications

Worldwide production of R-22 in 2008 was about 800 Gg per year, up from about 450 Gg per year in 1998, with most production in developing countries. R-22 use is increasing in developing countries, largely for air conditioning applications. Air conditioning sales are growing 20% annually in India and China.

R-22 is prepared from chloroform:

Dichlorodifluoromethane

Dichlorodifluoromethane (R-12) is a colorless gas usually sold under the brand name Freon-12, and a chlorofluorocarbon halomethane (CFC) used as a refrigerant and aerosol spray propellant. Complying with the Montreal Protocol, its manufacture was universally banned in 1996 due to concerns about its damaging impact to the ozone layer. Its only allowed usage is as fire retardant in submarines and aircraft. It is soluble in many organic solvents. Dichlorodifluoromethane was one of the original propellants for Silly String. R-12 cylinders are colored white.

Preparation

It can be prepared by reacting carbon tetrachloride with hydrogen fluoride in the presence of a catalytic amount of antimony pentachloride:

This reaction can also produce trichlorofluoromethane (CCl₃F), chlorotrifluoromethane (CClF₃) and tetrafluoromethane (CF₄).

History

Charles (Boss) Kettering, vice president of General Motors Research Corporation, was seeking a refrigerant replacement that would be colorless, odorless, tasteless, nontoxic, and nonflammable. He assembled a team that included Thomas Midgley, Jr., Albert Leon Henne and Robert McNary. From 1930 to 1935 they developed dichlorodifluoromethane (CCl₂F₂ or R12), trichlorofluoromethane (CCl₃F or R11), chlorodifluoromethane (CHClF₂ or R22), trichlorotrifluoroethane (CCl₂FCClF₂ or R113), and dichlorotetrafluoroethane (CClF₂CClF₂ or R114), through Kinetic Chemicals which was a joint venture between DuPont and General Motors.