Chlorofluorocarbons

WT Tsai, National Pingtung University of Science and Technology, Pingtung, Taiwan

Ó 2014 Elsevier Inc. All rights reserved.

Background physiologically inert, they can cause cardiac sensitization (i.e.,

It is recognized that nontoxic and nonflammable refrigerants
(Freon or chlorofluorocarbon (CFC)) were commercialized in
the manufacture of chlorofluoro- derivatives of methane and
ethane until the 1930s. Since that time, studies on the synthesis
of CFCs and their applications have progressed in many direc-
tions, such as aerosol, blowing agent for foam manufacture, fire
extinguisher, cleaning solvent, and refrigerant. Due to the
potential environmental and health effects of ozone depletion
and greenhouse effect, the use of Freons has been reduced by
international agreements since the end of the 1980s. Under
a treaty known as the Montreal Protocol on Substances that
Deplete the Ozone Layer, which was first established in 1987,
several interim replacements for CFCs were thus developed in
the 1990s, i.e., partially or fully fluorinated or partially chloro-
fluorinated alkanes, including hydrochlorofluorocarbons
(HCFCs), hydrofluorocarbons (HFCs) and perfluorocarbons
(PFCs). Table 1 lists the chemical identities and the information
on ozone depletion potential (ODP), global warming potential
(GWP), and partition property of common CFCs, including
trichlorofluoromethane (CFC-11), dichlorodifluoromethane
(CFC-12), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),
1,2-dichlorotetrafluoroethane (CFC-114), and chloropenta-
fluoroethane (CFC-115).
Obviously, these CFCs contain only the elements chlorine,
fluorine, and carbon. Thus, they are usually colorless gases or
liquids that evaporate easily at room temperatures. They are
generally unreactive and stable, nontoxic, and nonflammable.
It means that the atmosphere is the most likely fate for their
accumulations of emissions. CFCs are also a part of the group
of chemicals known as the volatile organic compounds. On
the other hand, it can be seen in Table 1 that the values of
log Kow for CFCs are below 3.5, showing that these fluoro-
carbons have very low potential bioaccumulation in the
environment. Herein, some CFCs, including chlorotrifluoro-
methane (CFC-13), 1,1,1,2-tetrachloro-2,2-difluoroethane
(CFC-112a), and 1,1,2,2-tetrachloro-1,2-difluoroethane
(CFC-112), are not discussed.
Mode of Action
CFCs are characterized by high chemical and thermal stabili-
ties, nonflammability, and low toxicity. Although CFCs are
sensitization of the heart to the body’s adrenalin) at high
concentrations (e.g., above 10% in air). This can lead to cardiac
arrhythmia, resulting in irregular heartbeat and sometimes
cardiac arrest.
Major Uses
The chemical inertness, thermal stability, low toxicity, and
nonflammability of these CFCs coupled with their unique
physical properties are used in many application fields,
including refrigerant for air conditioning, aerosol (propellant),
blowing agent for foam manufacture, fire extinguisher, clean-
ing agent, dielectric fluid, and ion implantation of semi-
conductor device. However, it should be noted that the
timetable of phase-out of these compounds was regulated by
the Montreal protocol (i.e., the production of CFCs ended by
1 January 1996 and their applications banned).
Environmental Hazards
GWP expresses the relative increase in earthward IR radiation
flux due to the emission of organic compounds. Notably, all
CFCs have high GWP values relative to the reference
compound, carbon dioxide (seen in Table 1). Furthermore,
these saturated halocarbons are considered not easily biode-
gradable based on the data of octanol/water partition coeffi-
cients also listed in Table 1. With respect to ecotoxicity, it was
also revealed to be not very toxic to aquatic organisms (i.e.,
algae, water fleas, and fish) and terrestrial plants. For example,
CFC-113, which was one of the most used solvents, shows
a very low toxicity toward aquatic species such as Daphnia
and fish. As described, the most significant environmental
hazard for CFCs should be the ozone depletion, which is
caused by chlorine molecules in these so-called ozone-
depleting substances that migrate to the stratosphere and then
react catalytically with ozone, thus destroying it. In addition,
from the view of the effect on air quality, CFCs have been listed
as having ‘negligible photochemical reactivity’ and do not
contribute to smog formation and ground-level ozone. There-
fore, they are exempt from volatile organic compound regula-
tions according to the US Clean Air Act Amendments of 1990.

Table 1 Environmental properties of common chlorofluorocarbons (CFCs)

CFCs (abbrev.) CAS no. Molecular formula Mol. wt. (g mol
1) Lifetime (years) ODPa GWPb Log Kow

Trichlorofluoromethane (CFC-11) 75-69-4 CCl3F 137.38 45 1.0 4750 2.53

Dichlorodifluoromethane (CFC-12) 75-71-8 CCl2F2 120.91 100 1.0 10 900 2.16
1,1,2-Trichloro-1,2,2-trifluoroethane (CFC-113) 76-13-1 CCl2FCClF2 187.40 85 0.8 6130 3.16
1,2-Dichlorotetrafluoroethane (CFC-114) 76-14-2 CClF2CClF2 170.93 300 1.0 10 000 2.82
Chloropentafluoroethane (CFC-115) 76-15-3 CClF2CF3 154.47 1700 0.6 7370 2.30

Ozone depletion potential (relative to the ODP of CFC-11 ¼ 0) in Montreal Protocol.

a

Global warming potential with 100-year time horizon (relative to GWP of CO2 ¼ 1).
b

Encyclopedia of Toxicology, Volume 1 http://dx.doi.org/10.1016/B978-0-12-386454-3.01118-0 883

884 Chlorofluorocarbons
Table 2 Toxicity data and exposure limits of common chlorofluorocarbons (CFCs)
CFCs LC50a (ppm) LOELb (ppm) OSHA-PELc (ppm)
CFC-11 26 200 5000 1000
CFC-12 760 000 50 000 1000
CFC-113 52 000 5000 1000
CFC-114 600 000 25 000 1000
CFC-115 ＞800 000 150 000 1000
a
LC50: Lethal concentration for 50% of test animals (rat).
b
LOEL: Lowest observed effect level at which sensitization occurs in dog with epinephrine challenge.
c
OSHA-PEL: US Occupational Safety and Health Administration permissible exposure limit based on 8-h time-weighted average.
d
ACGIH-TLV: American Conference of Governmental Industrial Hygienists-Threshold Limit Value based on 8-h time-weighted average.
Exposure Routes and Pathways
Inhalation (pulmonary route) is the main source of exposure to
CFCs. Skin absorption or contact (dermal exposure) and eye
contact may also occur. Because they are no longer used as
refrigerants and blowing agents, human exposure to CFCs may
occur via inhalation from accidental leaks or spills from
a refrigeration system of recycling system for electronic appli-
ances where they are still used.
Acute (Short-Term) Health Effects
Due to the physiochemical properties of CFCs, there is only
a low potential for human toxicity based on the results of
mammalian (i.e., rat) tests, and no significant acute health risk
is expected. Briefly, the biotransformation of CFCs has been
shown to undergo cytochrome P450-catalyzed oxidation or
reduction reactions. The formed acyl halides are further
hydrolyzed to give excretable haloacetic acid (e.g., trifluoro-
acetic acid) in urine. Although CFCs are physiologically inert,
exposure to pressurized CFCs like liquid nitrogen, such as may
occur with a refrigerant leak, can cause frostbite as well as to the
upper airway if inhaled, possibly resulting in asphyxiation and
cardiac sensitization (i.e., sensitization of the heart to the body’s
adrenalin) at high concentrations. The data on lowest observed
effect level and lethal concentration for 50% of specimens
(LC50) for common CFCs are also listed in Table 2. It should be
noted that repair of air-conditioning systems could involve
welding operations and possibly cause the occupational expo-
sure to decomposition toxic products, including hydrogen
fluoride (HF), hydrogen chloride (HCl), carbon monoxide
(CO), phosgene (COCl2), and carbonyl fluoride (COF2).
Chronic (Long-Term) Health Effects
In general, occupational workers exposed to CFCs at the
exposure standards/limits (described below) showed no
adverse health effects. In experimental animals exposed to
CFCs for long-term tests, no significant effects were seen.
Regarding the carcinogenic, reproductive, and developmental
effects of CFCs, their potential for chronic effects is low.
Exposure Standards/Limits
Basically, CFCs have only a low potential for toxicity, and are
considered not readily biodegradable, with very low
ACGIH-TLVd (ppm) TLV-basis
1000 Cardiac sensitization
1000 Cardiac sensitization
1000 Central nervous system impairment
1000 Pulmonary function
1000 Cardiac sensitization
ecotoxicity. Thus, the exposure limits for these chemicals, based
on the permissible exposure limit by the US Occupational
Safety and Health Administration and the threshold limit value
(TLV) by the American Conference of Governmental Industrial
Hygienists, are mostly set at 1000 ppm, as shown in Table 2.
However, there are some exceptions as in the cases of CFC-112a
and CFC-112. They will cause liver and kidney damage to
experimental animals subjected to repeated exposure at high
concentration; therefore, TLV-time-weighted average values of
100 ppm and 50 ppm are set for CFC-112a and CFC-112,
respectively.
See also: Aerosols; Ozone; Global Climate Change and
Environmental Toxicology.
Further Reading
American Conference of Governmental Industrial Hygienists, 2009. Documentation of
the Threshold Limit Values and Biological Exposure Indices. ACGIH, Cincinnati,
Ohio, USA.
Dekant, W., 1996. Toxicology of chlorofluorocarbon replacements. Environ. Health
Perspect. 104 (Suppl. 1), 75–83.
Mackay, D., Shiu, W.Y., Ma, K.C., Lee, S.C., 2006. Handbook of Physical-chemical
Properties and Environmental Fate for Organic Chemicals, second ed. CRC
Press, Boca Raton, FL, USA.
National Institute for Occupational Safety and Health, 2004. NIOSH Pocket Guide to
Chemical Hazards. NIOSH, Atlanta, GA, USA.
Sekiya, A., Yamabe, M., Tokuhashi, K., Hibino, Y., Imasu, R., Okamoto, H., 2006.
Evaluation and selection of CFC alternatives. In: Tressaud, A. (Ed.), Fluorine and the
Environment: Atmospheric Chemistry, Emissions, & Lithosphere. Elsevier,
Amsterdam, pp. 33–87.
United Nations Environment Programme, 2011. Scientific Assessment of Ozone
Depletion: 2010. UNEP, Geneva.
Relevant Websites
http://www.inchem.org/ – Fully Halogenated Chlorofluorocarbons (Environmental
Health Criteria 113).
http://toxnet.nlm.nih.gov/ – National Library of Medicine’s Toxicology Data Network
(TOXNET).
http://www.des.nh.gov/ – New Hampshire Department of Environmental Services,
Chlorofluorocarbons (CFCs): Health Information Summary (ARD-EHP-34).