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What Is A Refrigerant?

At the end of the last millennium, there were many “Top Ten” lists made, including one listing the greatest invention of the twentieth century. Along with space flight and computers, refrigeration made the top ten because without refrigeration, food preservation would not be possible. In addition, there could not be high rise office buildings or modern health care facilities. Webster’s dictionary defines refrigerants as “a substance used in a refrigerating cycle or directly such as ice for cooling”. A person from outside the HVAC industry might describe a refrigerant as some kind of fluid used in an air conditioner. Many within the HVAC industry would immediately think of CFCs (Chlorofluorocarbons). All these definitions are accurate, but refrigerants are much more than that. Water is the refrigerant used in absorption chillers. Carbon Dioxide (CO2) and Ammonia (NH3) are known as “natural” refrigerants. Flammable substances such as propane and isobutane are also used as refrigerants. To this group, CFCs, HCFCs and HFCs can be added. ASHRAE Standard 34, Designation and Safety Classification of Refrigerants, lists over 100 refrigerants, although many of these are not used on a regular commercial HVAC basis. Refrigerants are chemical substances. Some substances known as refrigerants (e.g. R-141b) are used in diverse applications such as a foam blowing agent, which has little to do with “cooling spaces”.

Refrigerant History
Mechanical refrigeration has been around since the mid-nineteenth century. The first practical machine was built by Jacob Perkins in 18341. It was based on using ether as a refrigerant in a vapor compression circuit. Carbon Dioxide (CO2) was first used as a refrigerant in 1866 and Ammonia (NH3) in 1873. Other chemicals used as vapor compression refrigerants included chymgene (petrol ether and naphtha), sulfur dioxide (R-764) and methyl ether. Their applications were limited to industrial processes. Most food preservation was accomplished by using blocks of ice collected during the winter and stored or manufactured through an industrial process. By the beginning of the twentieth century, refrigeration systems were being used to provide air conditioning in major building projects. The Milam Building in San Antonio, Texas was the first high-rise office building to be completely air conditioned2. In 1926, Thomas Midgely developed the first CFC (Chlorofluorocarbons), R-12. CFCs were nonflammable, non-toxic (when compared to Sulfur Dioxide) and efficient. Commercial production began in 1931 and quickly found a home in refrigeration. Willis Carrier developed the first centrifugal chiller for commercial use and the era of refrigeration and air conditioning began. For technical reasons that will be discussed later, several refrigerants became very popular in air conditioning including CFC-11, CFC-12, CFC-113, CFC-114 and HCFC-22. While the fledgling air conditioning industry grew into a multi billion dollar industry, very little changed on the refrigerant front. By 1963, these refrigerants represented 98% of the organic fluorine industry. By the mid 1970s, concerns began to surface about the thinning of the ozone layer and whether CFCs may be in part responsible. This led to the ratification of the Montreal Protocol in 1987 that required the phase out of CFCs and HCFCs. New solutions were developed with HFCs taking on a major role as refrigerants. HCFCs continued to be used as interim solutions and at the time of writing this document were beginning to be phased out. In the 1990s global warming arose as the new threat to the well being of the planet. While there are many contributors to global warming, refrigerants were again included in the discussion because air conditioning and refrigeration are significant energy users (about 1/3 of the energy in the USA is consumed in the operation of buildings) and many refrigerants are themselves greenhouse gases.
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Thevenot, R. 1979. A History of Refrigeration Throughout the World. International Institute of Refrigeration (IIR) 2 Pauken, M. May 1999. Sleeping Soundly on Summer Nights. ASHRAE Journal
4 Application Guide AG 31-007