Replacement of CFCs
as refrigerants
A. The first generation replacement of CFCs
as refrigerants (HCFC)
HCFCs used as substitutes for CFCs are listed in Table 2.
HCFCs are compounds containing carbon, hydrogen, chlorine and fluorine. The
HCFCs have shorter atmospheric lifetimes than CFCs and deliver less reactive
chlorine to the stratosphere where the "ozone layer" is found. Consequently,
it is expected that these chemicals will contribute much less to stratospheric
ozone depletion than CFCs. Because they still contain chlorine and have the
potential to destroy stratospheric ozone, they are viewed only as temporary
replacements for the CFCs.
HCFCs are less stable than CFCs because HCFC molecules contain carbon-hydrogen
bonds. Hydrogen is attacked by the hydroxyl radical in the lower part of the
atmosphere known as the troposphere. When HCFCs are oxidized in the troposphere,
the chlorine released typically combines with other chemicals to form compounds
that dissolve in water and ice and are removed from the atmosphere by precipitation.
When HCFCs become destroyed in this way their chlorine does not reach the stratosphere
and contribute to ozone destruction.
A certain portion of HCFC molecules released to the atmosphere will reach the
stratosphere and be destroyed there by photolysis (light-initiated decomposition).
The chlorine released in the stratosphere can then participate in ozone depleting
reactions as does chlorine liberated from the photolysis of CFCs. Because HCFCs
are degraded significantly by two mechanisms in the atmosphere (as opposed to
the CFCs which are destroyed almost exclusively by photolysis in the stratosphere),
and because photolysis rates of HCFCs are generally slower than those for CFCs,
proportionately less chlorine is released from HCFCs in the lower stratosphere
when compared to CFCs. These properties explain why HCFCs are expected to deplete
much less stratospheric ozone than equivalent amounts of CFCs. HCFCs phase-out
dates are shown in Figure 3.
![]() |
Figure
3: HCFC refrigerant phase-out dates (13) |
B. The second generation replacement of CFCs as refrigerants (HFCs)
Table 3: HFCs as alternative for CFCs |
| HFC-23 (CHF3) | HFC-143a (CF3CH3 ) |
| HFC-32(CH2F2 ) | HFC-152a (CH3CHF2) |
| HFC-43-10mee (CF3CHF2CHFCH2FCF3) | HFC-227ea (CF3CHFCF3) |
| HFC-125(CHF2CF3 ) | HFC-236fa (CF3CH2CF3 ) |
| HFC-134a (CH2FCF3 ) | HFC-245fa (CF3CH2CHF2) |
Hydrofluorocarbons (HFCs) are compounds containing carbon, hydrogen, and fluorine.
Certain chemicals within this class of compounds are viewed by industry and
the scientific community as acceptable alternatives to CFCs and HCFCs on a long-term
basis. Because the HFCs contain no chlorine they do not directly affect stratospheric
ozone. Furthermore, mechanisms for ozone destruction involving fragments produced
as HFCs are decomposed within the atmosphere (CF3 radicals) have been shown
to be insignificant.All HFCs have an ozone depletion potential of 0.
Like HCFCs, the HFCs contain hydrogen that is susceptible to attack by the hydroxyl
radical. Oxidation of HFCs by the hydroxyl radical is believed to be the major
destruction pathway for HFCs in the atmosphere. Atmospheric lifetimes of the
most commonly used HFCs (HFC-134a and HFC-152a) are limited to <12 years
because of this reaction.
Although it is believed HFCs will not deplete ozone within the stratosphere,
this class of compounds has other adverse environmental effects. It has been
postulated that extensive use of these chemicals in the future could contribute
significantly to enhanced radiative atmospheric heating. Also, a number of the
HFCs, for example HFC-134a, are expected to decompose in the atmosphere and
produce a long-lived chemical called trifluoroacetic acid (or TFA) that is known
to have adverse effects on certain biota. Concern over these effects may make
it necessary to regulate production and use of these compounds at some point
in the future. (14)
C. The third generation replacement of CFCs
as refrigerants
The third generation substitutes for CFCs are listed in Table
4.
D. The future replacement of CFCs as refrigerants
Looking further down the road, carbon dioxide may someday replace today’s
refrigerants. Though carbon dioxide is a "greenhouse gas" that may
contribute to global warming, it is non-toxic, non-flammable, cheap and abundant.
But to work as a refrigerant, carbon dioxide must be run at extremely high pressures
- up to several thousand psi! As long as the gas is safely contained at high
pressure, it works pretty well as a refrigerant. But such high pressures pose
a potential danger to technicians who must ultimately work on such systems.
Someday a perfect air conditioner may use no refrigerant whatsoever. Some time
back, the Rovac Corporation in Rockledge, FL, announced it had developed a revolutionary
A/C system that required no refrigerant at all, and used air itself as the working
medium. The Rovac system used a "circulator" that was essentially
an expander rather than a compressor. By expanding the volume of air, the drop
in pressure produced a corresponding drop in temperature. The system supposedly
required 35 to 40% less power than a refrigerant-based A/C system and provided
equivalent cooling. Mitsubishi has licensed rights to the technology and was
investigating it further. That was 20 years ago. We’re still waiting.
Ten years ago, the Naval Postgraduate School in Monterey, CA, claimed it had
developed a refrigeration process using an acoustic generator. Sound waves were
used to create pressure changes that had a chilling effect. No word as to what
ever happened to this technology.
Although there are a lot of substitutes for CFCs as refrigerants, scientists
continue to research new substitutes, which are less expensive, less destructive
for ozone layer and more practical for industry. (16)