Refrigerant

A refrigerant is a working fluid used in the refrigeration cycle of air conditioning systems and heat
pumps where in most cases they undergo a repeated phase transition from a liquid to a gas and
back again. Refrigerants are heavily regulated due to their toxicity, flammability and the
contribution of CFC and HCFC refrigerants to ozone depletion and that of HFC refrigerants to
climate change.

A DuPont R-134a refrigerant

Refrigerants are used in a direct expansion (DX) system to transfer energy from one environment
to another, typically from inside a building to outside (or vice versa) commonly known as an "air
conditioner" or "heat pump". Refrigerants can carry per kg 10 times more energy than water and
50 times more than air.

In some countries, refrigerants are controlled substances due to high pressures (700–1,000 kPa
(100–150 psi)), extreme temperatures (−50 °C [−58 °F] to over 100 °C [212 °F]), flammability (A1
class non-flammable, A2/A2L class flammable and A3 class extremely flammable/explosive) and
toxicity (B1-low, B2-medium & B3-high), as classified by ISO 817 & ASHRAE 34.

Refrigerants must only be handled by qualified/certified engineers to the relevant classes of

refrigerant (in the UK, C&G 2079 for A1-class, and C&G 6187-2 for A2/A2L & A3 class refrigerants).

History

The observed stabilization of HCFC concentrations

(left graphs) and the growth of HFCs (right graphs) in
earth's atmosphere.

The first air conditioners and refrigerators employed toxic or flammable gases, such as ammonia,
sulfur dioxide, methyl chloride, or propane, that could result in fatal accidents when they leaked.[1]

In 1928 Thomas Midgley Jr. created the first non-flammable, non-toxic chlorofluorocarbon gas,
Freon (R-12). The name is a trademark name owned by DuPont (now Chemours) for any
chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC), or hydrofluorocarbon (HFC) refrigerant.
Following the discovery of better synthesis methods, CFCs such as R-11,[2] R-12,[3] R-123[2] and R-
502[4] dominated the market.
Phasing out of CFCs
In the early 1980s, scientists discovered that CFCs were causing major damage to the ozone layer
that protects the earth from ultraviolet radiation, and to the ozone holes over polar regions. This
led to the signing of the Montreal Protocol in 1987 which aimed to phase out CFCs and HCFC[5] but
did not address the contributions that HFCs made to climate change. The adoption of HCFCs such
as R-22,[6][7][8] and R-123[2] was accelerated and so were used in most U.S. homes in air
conditioners and in chillers[9] from the 1980s as they have a dramatically lower Ozone Depletion
Potential (ODP) than CFCs, but their ODP was still not zero which led to their eventual phase-out.

Hydrofluorocarbons (HFCs) such as R-134a,[10][11] R-143a, R-407A,[12] R-407C,[13] R-404A,[4] R-

410A[14] (a 50/50 blend of R-125/R-32) and R-507[15][16] were promoted as replacements for CFCs
and HCFCs in the 1990s and 2000s. HFCs were not ozone-depleting but did have global warming
potentials (GWPs) thousands of times greater than CO2 with atmospheric lifetimes that can extend
for decades. This in turn, starting from the 2010s, led to the adoption in new equipment of
Hydrocarbon and HFO (hydrofluoroolefin) refrigerants R-32,[17] R-290,[18] R-600a,[18] R-454B,[19] R-
1234yf,[20][21] R-514A,[22] R-744 (CO2),[23] R-1234ze(E)[24] and R-1233zd(E),[25] which have both an
ODP of zero and a lower GWP. Hydrocarbons and CO2 are sometimes called natural refrigerants
because they can be found in nature.

The environmental organization Greenpeace provided funding to a former East German

refrigerator company to research alternative ozone- and climate-safe refrigerants in 1992. The
company developed hydrocarbon mixes such as isopentane and isobutane, propane and
isobutane, or pure isobutane,[26] called "Greenfreeze", but as a condition of the contract with
Greenpeace could not patent the technology, which led to their widespread adoption by other
firms.[27][28][29] Policy and political influence by corporate executives resisted change however,[30][31]
citing the flammability and explosive properties of the refrigerants,[32] and DuPont together with
other companies blocked them in the U.S. with the U.S. EPA.[33][34]

Beginning on 14 November 1994, the U.S. Environmental Protection Agency restricted the sale,
possession and use of refrigerants to only licensed technicians, per rules under sections 608 and
609 of the Clean Air Act.[35] In 1995, Germany made CFC refrigerators illegal.[36]

In 1996 Eurammon, a European non-profit initiative for natural refrigerants, was established and
comprises European companies, institutions, and industry experts.[37][38][39]

In 1997, FCs and HFCs were included in the Kyoto Protocol to the Framework Convention on
Climate Change.
In 2000 in the UK, the Ozone Regulations[40] came into force which banned the use of ozone-
depleting HCFC refrigerants such as R22 in new systems. The Regulation banned the use of R22 as
a "top-up" fluid for maintenance from 2010 for virgin fluid and from 2015 for recycled fluid.

Addressing greenhouse gases

With growing interest in natural refrigerants as alternatives to synthetic refrigerants such as CFCs,
HCFCs and HFCs, in 2004, Greenpeace worked with multinational corporations like Coca-Cola and
Unilever, and later Pepsico and others, to create a corporate coalition called Refrigerants
Naturally!.[36][41] Four years later, Ben & Jerry's of Unilever and General Electric began to take steps
to support production and use in the U.S.[42] It is estimated that almost 75 percent of the
refrigeration and air conditioning sector has the potential to be converted to natural
refrigerants.[43]

In 2006, the EU adopted a Regulation on fluorinated greenhouse gases (FCs and HFCs) to
encourage to transition to natural refrigerants (such as hydrocarbons). It was reported in 2010 that
some refrigerants are being used as recreational drugs, leading to an extremely dangerous
phenomenon known as inhalant abuse.[44]

From 2011 the European Union started to phase out refrigerants with a global warming potential
(GWP) of more than 150 in automotive air conditioning (GWP = 100-year warming potential of one
kilogram of a gas relative to one kilogram of CO2) such as the refrigerant HFC-134a (known as R-
134a in North America) which has a GWP of 1526.[45] In the same year the EPA decided in favour of
the ozone- and climate-safe refrigerant for U.S. manufacture.[27][46][47]

A 2018 study by the nonprofit organization "Drawdown" put proper refrigerant management and
disposal at the very top of the list of climate impact solutions, with an impact equivalent to
eliminating over 17 years of US carbon dioxide emissions.[48]

In 2019 it was estimated that CFCs, HCFCs, and HFCs were responsible for about 10% of direct
radiative forcing from all long-lived anthropogenic greenhouse gases.[49] and in the same year the
UNEP published new voluntary guidelines,[50] however many countries have not yet ratified the
Kigali Amendment.

From early 2020 HFCs (including R-404A, R-134a and R-410A) are being superseded: Residential
air-conditioning systems and heat pumps are increasingly using R-32. This still has a GWP of more
than 600. Progressive devices use refrigerants with almost no climate impact, namely R-290
(propane), R-600a (isobutane) or R-1234yf (less flammable, in cars). In commercial refrigeration
also CO2 (R-744) can be used.

Requirements and desirable

properties
A refrigerant needs to have: a boiling point that is somewhat below the target temperature
(although boiling point can be adjusted by adjusting the pressure appropriately), a high heat of
vaporization, a moderate density in liquid form, a relatively high density in gaseous form (which
can also be adjusted by setting pressure appropriately), and a high critical temperature. Working
pressures should ideally should be containable by copper tubing a commonly available material.
Extremely high pressures should be avoided.

The ideal refrigerant would be: non-corrosive, non-toxic, non-flammable, with no ozone depletion
and global warming potential. It should preferably be natural with well-studied and low
environmental impact. Newer refrigerants address the issue of the damage that CFCs caused to
the ozone layer and the contribution that HCFCs make to climate change, but some do raise issues
relating to toxicity and/or flammability.[51]

Common refrigerants

Refrigerants with very low climate

impact
With increasing regulations, refrigerants with a very low global warming potential are expected to
play a dominant role in the 21st century,[52] in particular, R-290 and R-1234yf. Starting from almost
no market share in 2018,[53] low GWPO devices are gaining market share in 2022.
 GWP GWP
Code Chemical Name [54]
Status Commentary
20yr 100yr[54]

Low cost, widely

available and
efficient. They also
have zero ozone
depletion potential.
Despite their
flammability, they are
increasingly used in
domestic
refrigerators and heat
Increasing pumps. In 2010,
R-290 C3 H 8 Propane 3.3[55]
use about one-third of all
household
refrigerators and
freezers
manufactured
globally used
isobutane or an
isobutane/propane
blend, and this was
expected to increase
to 75% by 2020.[56]

Widely
R-600a HC(CH3)3 Isobutane 3.3 See R-290.
used

R-717 NH3 Ammonia 0 0[57] Widely Commonly used

used before the
popularisation of
CFCs, it is again
being considered but
does suffer from the
disadvantage of
toxicity, and it
requires corrosion-
resistant
components, which
 GWP GWP
Code Chemical Name [54]
Status Commentary
20yr 100yr[54]

restricts its domestic

and small-scale use.
Anhydrous ammonia
is widely used in
industrial
refrigeration
applications and
hockey rinks because
of its high energy
efficiency and low
cost.

Less performance
but also less
flammable than R-
R-
290.[52] GM
1234yf 2,3,3,3-
C 3 H 2 F4 <1 announced that it
HFO- Tetrafluoropropene
would start using
1234yf
"hydro-fluoro olefin",
HFO-1234yf, in all of
its brands by 2013.[58]

R-744 CO2 Carbon dioxide 1 1 In use Was used as a

refrigerant prior to
the discovery of CFCs
(this was also the
case for propane)[1]
and now having a
renaissance due to it
being non-ozone
depleting, non-toxic
and non-flammable.
It may become the
working fluid of
choice to replace
current HFCs in cars,
supermarkets, and
heat pumps such as
 GWP GWP
Code Chemical Name [54]
Status Commentary
20yr 100yr[54]

EcoCute. Coca-Cola
has fielded CO2-
based beverage
coolers and the U.S.
Army is considering
CO2
refrigeration.[59][60]
Due to the need to
operate at pressures
of up to 130 bars
(1,900 psi;
13,000 kPa), CO2
systems require
highly resistant
components,
however these have
already been
developed for mass
production in many
sectors.
Most used

Global
warming GWP
Code Chemical Name Status Commentary
potential 100yr[54]
20yr[54]

Promoted as
climate-friendly
substitute for R-
134a and R-410A,
but still with high
climate impact. Has
excellent heat
transfer and
pressure drop
R-32 Widely performance, both
CH2F2 Difluoromethane 2430 677
HFC-32 used in condensation
and
vaporisation.[61] It
has an atmospheric
lifetime of nearly 5
years.[62] Currently
used in residential
and commercial
air-conditioners
and heat pumps.

R-134a CH2FCF3 1,1,1,2- 3790 1550 Widely Most used in 2020

HFC- Tetrafluoroethane used for hydronic heat
134a pumps in Europe
and the United
States in spite of
high GWP.[53]
Commonly used in
automotive air
conditioners prior
 Global
warming GWP
Code Chemical Name Status Commentary
potential 100yr[54]
20yr[54]

to phase out which

began in 2012.

Between Most used in split

50% R-32 / 50% R-
2430 (R-32) Widely heat pumps / AC by
R-410A 125 > 677
and 6350 Used 2018. Almost 100%
(pentafluoroethane)
(R-125) share in the USA.[53]
Banned / Phased out

Global
warming GWP
Code Chemical Name Status Commentary
potential 100yr[54]
20yr[54]

Production was banned

R-11 in developed countries
CCl3F Trichlorofluoromethane 6900 4660 Banned
CFC-11 by Montreal Protocol in
1996

Also known as Freon, a

widely used
chlorofluorocarbon
halomethane (CFC).
R-12 Production was banned
CCl2F2 Dichlorodifluoromethane 10800 10200 Banned
CFC-12 in developed countries
by Montreal Protocol in
1996, and in developing
countries (article 5
countries) in 2010.[63]

A widely used
hydrochlorofluorocarbon
(HCFC) and powerful
greenhouse gas with a
GWP equal to 1810.
R-22 Being
Worldwide production
HCFC- CHClF2 Chlorodifluoromethane 5280 1760 phased
of R-22 in 2008 was
22 out
about 800 Gg per year,
up from about 450 Gg
per year in 1998. R-
438A (MO-99) is a R-22
replacement.[64]

R-123 CHCl2CF3 2,2-Dichloro-1,1,1- 292 79 US Used in large tonnage

HCFC- trifluoroethane phase- centrifugal chiller
123 out applications. All U.S.
 Global
warming GWP
Code Chemical Name Status Commentary
potential 100yr[54]
20yr[54]

production and import

of virgin HCFCs will be
phased out by 2030,
with limited
exceptions.[65] R-123
refrigerant was used to
retrofit some chiller that
used R-11 refrigerant
Trichlorofluoromethane.
The production of R-11
was banned in
developed countries by
Montreal Protocol in
1996.[66]
Other

Global
warming GWP
Code Chemical Name Commentary
potential 100yr[54]
20yr[54]

R-152a
As a compressed air
HFC- CH3CHF2 1,1-Difluoroethane 506 138
duster
152a

Mixture of
difluoromethane and
A mixture of R-32, R-125,
R-407C pentafluoroethane
and R-134a
and 1,1,1,2-
tetrafluoroethane

HFOs blend of
refrigerants
Difluoromethane and
Difluoromethane (R-32)
R-454B 2,3,3,3-
and 2,3,3,3-
Tetrafluoropropene
Tetrafluoropropene (R-
1234yf).[67][68][69][70]

An HFO/HFC blend
May replace R-134a as
R-513A (56% R-1234yf/44%R-
an interim alternative[71]
134a)

An hydrofluoroolefin
(HFO)-based refrigerant
HFO-1336mzz-
to replace R-123 in low
Z/trans-1,2-
R-514A pressure centrifugal
dichloroethylene (t-
chillers for commercial
DCE)
and industrial
applications.[72][73]
Refrigerant reclamation and
disposal
Coolant and refrigerants are found throughout the industrialized world, in homes, offices, and
factories, in devices such as refrigerators, air conditioners, central air conditioning systems (HVAC),
freezers, and dehumidifiers. When these units are serviced, there is a risk that refrigerant gas will
be vented into the atmosphere either accidentally or intentionally, hence the creation of technician
training and certification programs in order to ensure that the material is conserved and managed
safely. Mistreatment of these gases has been shown to deplete the ozone layer and is suspected
to contribute to global warming.[74]

With the exception of isobutane and propane (R600a, R441A and R290), ammonia and CO2 under
Section 608 of the United States' Clean Air Act it is illegal to knowingly release any refrigerants into
the atmosphere.[75][76]

Refrigerant reclamation is the act of processing used refrigerant gas which has previously been
used in some type of refrigeration loop such that it meets specifications for new refrigerant gas. In
the United States, the Clean Air Act of 1990 requires that used refrigerant be processed by a
certified reclaimer, which must be licensed by the United States Environmental Protection Agency
(EPA), and the material must be recovered and delivered to the reclaimer by EPA-certified
technicians.[77]
Classification of refrigerants

R407C pressure-enthalpy diagram,

isotherms between the two
saturation lines

Refrigerants may be divided into three classes according to their manner of absorption or
extraction of heat from the substances to be refrigerated:

Class 1: This class includes refrigerants

that cool by phase change (typically
boiling), using the refrigerant's latent
heat.

Class 2: These refrigerants cool by

temperature change or 'sensible heat',
the quantity of heat being the specific
heat capacity x the temperature change.
They are air, calcium chloride brine,
sodium chloride brine, alcohol, and
similar nonfreezing solutions. The
purpose of Class 2 refrigerants is to
receive a reduction of temperature from
Class 1 refrigerants and convey this lower
temperature to the area to be cooled.

Class 3: This group consists of solutions

that contain absorbed vapors of
liquefiable agents or refrigerating media.
These solutions function by nature of
their ability to carry liquefiable vapors,
which produce a cooling effect by the
absorption of their heat of solution. They
 can also be classified into many
categories.

R numbering system
The R- numbering system was developed by DuPont (which owned the Freon trademark), and
systematically identifies the molecular structure of refrigerants made with a single halogenated
hydrocarbon. ASHRAE has since set guidelines for the numbering system as follows:[78]

R-X1X2X3X4

X1 = Number of unsaturated carbon-

carbon bonds (omit if zero)

X2 = Number of carbon atoms minus 1

(omit if zero)

X3 = Number of hydrogen atoms plus 1

X4 = Number of fluorine atoms

Series

R-xx Methane Series

R-1xx Ethane Series

 R-2xx Propane Series

R-4xx Zeotropic blend

R-5xx Azeotropic blend

R-6xx Saturated hydrocarbons (except

for propane which is R-290)

R-7xx Inorganic Compounds with a

molar mass < 100

R-7xxx Inorganic Compounds with a

molar mass ≥ 100

Ethane Derived Chains

Number Only Most symmetrical isomer

Lower Case Suffix (a,b,c,etc.) indicates

increasingly unsymmetrical isomers
Propane Derived Chains

Number Only If only one isomer exists;

otherwise:

First lower case suffix (a-f):

a Suffix Cl2 central carbon
substitution

b Suffix Cl, F central carbon

substitution

c Suffix F2 central carbon

substitution

d Suffix Cl, H central carbon

substitution

e Suffix F, H central carbon

substitution
 f Suffix H2 central carbon
substitution

2nd Lower Case Suffix (a, b, c, etc.)

Indicates increasingly unsymmetrical
isomers

Propene derivatives

First lower case suffix (x, y, z):

x Suffix Cl substitution on central
atom

y Suffix F substitution on central

atom

z Suffix H substitution on central

atom

Second lower case suffix (a-f):

a Suffix =CCl2 methylene substitution
 b Suffix =CClF methylene
substitution

c Suffix =CF2 methylene substitution

d Suffix =CHCl methylene

substitution

e Suffix =CHF methylene substitution

f Suffix =CH2 methylene substitution

Blends

Upper Case Suffix (A,B,C,etc.) Same

blend with different compositions of
refrigerants

Miscellaneous

R-Cxxx Cyclic compound

R-Exxx Ether group is present

R-CExxx Cyclic compound with an ether
group

R-4xx/5xx + Upper Case Suffix

(A,B,C,etc.) Same blend with different
composition of refrigerants

R-6xx + Lower Case Letter Indicates

increasingly unsymmetrical isomers

7xx/7xxx + Upper Case Letter Same

molar mass, different compound

R-xxxxB# Bromine is present with the

number after B indicating how many
bromine atoms

R-xxxxI# Iodine is present with the

number after I indicating how many
iodine atoms

R-xxx(E) Trans Molecule

 R-xxx(Z) Cis Molecule
For example, R-134a has 2 carbon atoms, 2 hydrogen atoms, and 4 fluorine atoms, an empirical
formula of tetrafluoroethane. The "a" suffix indicates that the isomer is unbalanced by one atom,
giving 1,1,1,2-Tetrafluoroethane. R-134 (without the "a" suffix) would have a molecular structure of
1,1,2,2-Tetrafluoroethane.

The same numbers are used with an R- prefix for generic refrigerants, with a "Propellant" prefix
(e.g., "Propellant 12") for the same chemical used as a propellant for an aerosol spray, and with
trade names for the compounds, such as "Freon 12". Recently, a practice of using abbreviations
HFC- for hydrofluorocarbons, CFC- for chlorofluorocarbons, and HCFC- for
hydrochlorofluorocarbons has arisen, because of the regulatory differences among these groups.

Refrigerant safety
ASHRAE Standard 34, Designation and Safety Classification of Refrigerants, assigns safety
classifications to refrigerants based upon toxicity and flammability.

Using safety information provided by producers, ASHRAE assigns a capital letter to indicate
toxicity and a number to indicate flammability. The letter "A" is the least toxic and the number 1 is
the least flammable.[79]

See also

Brine (Refrigerant)

Section 608

List of Refrigerants
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title=Refrigerant&oldid=1212547926"

This page was last edited on 8 March 2024, at

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