Refrigerants

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 Refrigerants
Classification of refrigerants, Desirable properties of
refrigerants, environmental issues, Ozone depletion and
global warming, ODP, GWP & LCCP, selection of
environment friendly refrigerants, secondary
refrigerants, anti-freeze solutions, Zeotropes and
Azeotropes, refrigerant: recovery reclaims, recycle and
recharge

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• The working substance/agent in a refrigerating system that
absorbs, carries or releases heat from the place to be cooled or
refrigerated can be termed as a refrigerant.

• This heat transfer generally takes place through a phase change of

the refrigerant.

• Refrigerant is the fluid used for heat transfer in a

refrigerating system that absorbs heat during evaporation
from the region of low temperature and pressure, and releases heat
during condensation at a region of higher temperature and
pressure.

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• The thermodynamic efficiency of a refrigeration system depends
mainly on its operating temperatures.

• However, important practical issues such as the system design,

size, initial and operating costs, safety, reliability, and
serviceability etc. depend very much on the type of refrigerant
selected for a given application.

• Another important aspect is environmental issues such as ozone

layer depletion and global warming.

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 Primary Refrigerants
• Primary refrigerants are those fluids, which are used directly as
working fluids
• When used in compression or absorption systems, these fluids
provide refrigeration by undergoing a phase change process in the
evaporator
• The refrigerants used in home refrigerators like R-12, R 134a;
are primary refrigerants

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 Secondary Refrigerants
• Secondary refrigerants are those liquids, which are used for
transporting thermal energy from one location to other, sometimes
referred to as brines or antifreezes
• If the operating temperatures are above 0oC, then pure water can
also be used as secondary refrigerant, for example in large air
conditioning systems
• Antifreezes or brines are used when refrigeration is required at
sub-zero temperatures
• The secondary refrigerants do not undergo phase change as they
transport energy from one location to other
• The commonly used secondary refrigerants are water, sodium-
chloride brine, calcium chloride brine and propylene glycol

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 Criteria for Selection of Refrigerant
• Selection of refrigerant for a particular application is
based on the following requirements
– Thermodynamic and thermo-physical properties
– Environmental and safety properties, and
– Economics

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 Desirable properties of an Ideal Refrigerant
• It should have low boiling point and low freezing point.
• It should have low specific heat and high latent heat.
• The pressure required to be maintained in the evaporator and
condenser should be low enough to reduce the material cost
and must be positive to avoid leakage of air into the system.
• It should have low specific volume to reduce the size of the
compressor.
• It must have high thermal conductivity to reduce the area of
heat transfer in evaporator and condenser.
• It should be non flammable, non explosive and non
corrosive.
• It must have high miscibility with lubricating oil
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 Thermodynamic and thermo-physical
properties
Suction pressure:
• At a given evaporator temperature, the saturation pressure
should be above atmospheric for prevention of air or
moisture ingress into the system and ease of leak
detection. Higher suction pressure is better as it leads to
smaller compressor displacement
Discharge pressure:
• At a given condenser temperature, the discharge pressure
should be as small as possible to allow light-weight
construction of compressor, condenser etc
Pressure ratio:
• Should be as small as possible for high volumetric
efficiency and low power consumption
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Latent heat of vaporization:
• Should be as large as possible so that the required
mass flow rate per unit cooling capacity will be
small
Isentropic index of compression:
• Should be as small as possible so that the
temperature rise during compression will be small
Liquid specific heat:
• Should be small so that degree of sub cooling will
be large leading to smaller amount of flash gas at
evaporator inlet
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Vapour specific heat:
• Should be large so that the degree of
superheating will be small
Thermal conductivity:
• Thermal conductivity in both liquid as well as
vapour phase should be high for higher heat
transfer coefficients
Viscosity :
• Viscosity should be small in both liquid and
vapour phases for smaller frictional pressure
drops 13
 Environmental and safety properties
• In the early 1990s when alternative refrigerants were
implemented to replace CFC and HCFC, sponsored projects to
examine the impacts of the refrigerants on overall emissions of
greenhouse gases were taken up
• All conventional air conditioning and refrigeration systems can
lead to the emission of two different greenhouse gases (GHGs)
• First, the energy consumed by the systems, in the form of
electricity or the direct combustion of a fossil fuel, results in the
release of carbon dioxide
• Second, almost all of the refrigerants used in these applications
are GHGs
• If the refrigerant leaks out of the system during operation, is lost
during maintenance, or is not recovered when the system is
scrapped, it contributes to global warming 14
 Environmental and safety properties
• The two GHG contributions are expressed in Total Equivalent
Warming Impact (TEWI)
• The TEWI methodology explicitly seeks to identify both the
“direct” effect of greenhouse emissions from the product and the
“indirect” effect of carbon dioxide emissions related to the energy
consumption of the product

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 Environmental and safety properties
Ozone Depletion Potential (ODP):
• According to the Montreal protocol, the ODP of refrigerants
should be zero, i.e., they should be non-ozone depleting
substances.
• Refrigerants having non-zero ODP have either already been
phased-out (e.g. R 11, R 12) or will be phased-out in near-future
(e.g. R22).
• Since ODP depends mainly on the presence of chlorine or
bromine in the molecules, refrigerants having either chlorine (i.e.,
CFCs and HCFCs) or bromine cannot be used under the new
regulations

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 Ozone Depletion
• The ozone layer is a belt of naturally occurring ozone gas that sits
9.3 to 18.6 miles (15 to 30 kilometers) above Earth and serves as
a shield from the harmful ultraviolet B radiation emitted by the
sun
• Ozone is a highly reactive molecule that contains three oxygen
atoms
• It is constantly being formed and broken down in the high
atmosphere, 6.2 to 31 miles (10 to 50 kilometers) above Earth, in
the region called the stratosphere
• The ozone layer is deteriorating due to the release of pollution
containing the chemicals chlorine and bromine
• Such deterioration allows large amounts of ultraviolet B rays to
reach Earth, which can cause skin cancer and cataracts in humans
and harm animals as well
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 Ozone Depletion
• Chlorofluorocarbons (CFCs), chemicals found mainly in spray
aerosols heavily used by industrialized nations for much of the
past 50 years, are the primary culprits in ozone layer breakdown
• When CFCs reach the upper atmosphere, they are exposed to
ultraviolet rays, which causes them to break down into substances
that include chlorine
• The chlorine reacts with the oxygen atoms in ozone and rips apart
the ozone molecule

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Global Warming Potential (GWP):
• Refrigerants should have as low a GWP value as possible to
minimize the problem of global warming.
• Refrigerants with zero ODP but a high value of GWP (e.g.
R134a) are likely to be regulated in future
• Global Warming is the increase of Earth's average surface
temperature due to effect of greenhouse gases, such as carbon
dioxide emissions from burning fossil fuels or from deforestation,
which trap heat that would otherwise escape from Earth
• Human beings have increased the CO2 concentration in the
atmosphere by about thirty percent, which is an extremely
significant increase
• Combustion of Fossil Fuels, for electricity generation,
transportation, and heating, and also the manufacture of cement,
all result in the total worldwide emission of about 22 billion tons
of carbon dioxide to the atmosphere each year 19
Global Warming Impacts:
• Rising Seas
• Changes in rainfall patterns --- droughts and fires in some areas,
flooding in other areas.
• Increased likelihood of extreme events--- such as flooding,
hurricanes, etc.
• Melting of the ice caps --- loss of habitat near the poles.
• Melting glaciers - significant melting of old glaciers is already
observed.
• Widespread vanishing of animal populations --- following
widespread habitat loss.
• Spread of disease --- migration of diseases such as malaria to new,
now warmer, regions.
• Bleaching of Coral Reefs due to warming seas and acidification
due to carbonic acid formation
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Total Equivalent Warming Index (TEWI):
• The factor TEWI considers both direct (due to release into
atmosphere) and indirect (through energy consumption)
contributions of refrigerants to global warming.
• Naturally, refrigerants with as a low a value of TEWI are
preferable from global warming point of view

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Life Cycle Climate Performance (LCCP):
• Life Cycle Climate Performance (LCCP) is an evolving
method to evaluate the carbon footprint and global warming
impact of heating, ventilation, air conditioning (AC),
refrigeration systems, and potentially other applications such
as thermal insulating foam
• It is calculated as the sum of direct, indirect, and embodied
greenhouse gas (GHG) emissions generated over the lifetime
of the system “from cradle to grave,” i.e. from manufacture
to disposal
• LCCP is more inclusive than previous metrics such as Total
Equivalent Warming Impact (TEWI), which considers direct
and indirect GHG emissions but overlooks embodied
emissions
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Life Cycle Climate Performance (LCCP):
• Direct emissions include all climate forcing effects from
the release of refrigerants into the atmosphere, including
annual leakage and losses during service and disposal of
the unit
• Indirect emissions include the climate forcing effects of
GHG emissions from the electricity powering the
equipment
• The embodied emissions include the climate forcing
effects of the manufacturing processes, transport, and
installation for the refrigerant, materials, and equipment,
and for recycle or other disposal of the product at end of
its useful life
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Toxicity:
• Ideally, refrigerants used in a refrigeration system should be non-
toxic.
• However, all fluids other than air can be called as toxic as they
will cause suffocation when their concentration is large enough.
• Thus toxicity is a relative term, which becomes meaningful only
when the degree of concentration and time of exposure required
to produce harmful effects are specified

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Flammability:
• The refrigerants should preferably be non-flammable and non-
explosive.
• For flammable refrigerants special precautions should be taken to
avoid accidents

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Chemical stability:
• The refrigerants should be chemically stable as long as they are
inside the refrigeration system

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Miscibility with lubricating oils:
• Oil separators have to be used if the refrigerant is not miscible
with lubricating oil (e.g. ammonia).
• Refrigerants that are completely miscible with oils are easier to
handle (e.g. R12).
• However, for refrigerants with limited solubility (e.g. R 22)
special precautions should be taken while designing the system to
ensure oil return to the compressor

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Ease of leak detection:
• In the event of leakage of refrigerant from the system, it should be
easy to detect the leaks

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 Classification and Designations of Refrigerants

Since a large number of refrigerants have been

developed over the years for a wide variety of
applications, a numbering system has been adopted
to designate various refrigerants.
From the number one can get some useful
information about the type of refrigerant, its
chemical composition, molecular weight etc.
All the refrigerants are designated by R (or CFC,
HCFC, HFC and HC) followed by a unique number.
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 Designations of Refrigerants
Hydrocarbons – For a compound derived from a saturated
hydrocarbon denoted by the chemical formula
CmHnFpClq - the designation is R (m-1)(n+1)(p)

These are represented by a three digit nomenclature. Here, the first

digit represents the number of carbon atoms in the compound
minus one, the second digit stands for the number of hydrogen
atoms plus one while the third digit stands for the number of
fluorine atoms. The remaining atoms are chlorine.

CCl3F (Trichloro monofluoro methane) - R 11

CCl2F2 (Dichloro difluoro methane) - R 12
CHClF2 (Monochloro difluoro methane) - R 22
Propane (C3H8) - R 290
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In case of butane and higher hydrocarbons, the
prescribed method cannot be used. Accordingly
they are assigned the designations arbitrarily as
R 600
n-butane (C4H10) - R 600
iso-butane (CH3) 3CH - R 600a

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Unsaturated compounds, are distinguished by
putting the digit 1 before (m-1), thus

Ethylene - R 1150

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Inorganic refrigerants - These are designated by
number 7 followed by the molecular weight of the
refrigerant (rounded-off)

Ex: Ammonia: Molecular weight is 17, the

designation is R 717

Carbon dioxide: Molecular weight is 44, the

designation is R 744

Water: Molecular weight is 18, the designation is R

718

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Mixtures - Azeotropic mixtures are designated by 500
series, where as Zeotropic refrigerants (e.g. non-
azeotropic mixtures) are designated by 400 series.

Azeotropic mixtures:

R 500: Mixture of R 12 (73.8 %) and R 152a (26.2%)

R 502: Mixture of R 22 (48.8 %) and R 115 (51.2%)

R 503: Mixture of R 23 (40.1 %) and R 13 (59.9%)

R 507A: Mixture of R 125 (50%) and R 143a (50%)

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Zeotropic mixtures:

R 404A : Mixture of R 125 (44%), R 143a (52%)

and R 134a (4%)

R 407A : Mixture of R 32 (20%), R 125 (40%) and

R 134a (40%)

R 407B : Mixture of R 32 (10%), R 125 (70%) and

R 134a (20%)

R 410A : Mixture of R 32 (50%) and R 125 (50%)

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 Montreal Protocol
Adopted in 1987, the Montreal Protocol on Substances that Deplete
the Ozone Layer legally enforces the phase-out of the production and
use of ozone depleting substances - chemicals often used in
refrigeration, air-conditioning, foam manufacturing, aerosol
production, and fire extinguishing
The Montreal Protocol has, contributed to a significant drop in total
global production and consumption of ozone depleting substances
used in agricultural, consumer and industrial sectors around the
world. It has also generated climate benefits as some of these
substances are greenhouse gases
Since 2010, the agenda of the Protocol has focused on the phase-out
of hydrochlorofluorocarbons (HCFCs), an ozone-depleting susbtance
mainly used in cooling and refrigeration applications, and in the
manufacture of foam products
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 Kyoto Protocol
The Kyoto protocol was the first agreement between nations to
mandate country-by-country reductions in greenhouse-gas emissions.
Kyoto emerged from the UN Framework Convention on Climate
Change (UNFCCC), which was signed by nearly all nations at the
1992 mega-meeting popularly known as the Earth Summit
The framework pledges to stabilize greenhouse-gas concentrations
"at a level that would prevent dangerous anthropogenic interference
with the climate system". To put teeth into that pledge, a new treaty
was needed, one with binding targets for greenhouse-gas reductions.
That treaty was finalized in Kyoto, Japan, in 1997, after years of
negotiations, and it went into force in 2005
Under Kyoto, industrialised nations pledged to cut their yearly
emissions of carbon, as measured in six greenhouse gases, by varying
amounts, averaging 5.2%, by 2012 as compared to 1990. That
equates to a 29% cut in the values that would have otherwise
occurred
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 Clean Development Mechanism
The Clean Development Mechanism (CDM), defined in Article 12 of
the Protocol, allows a country with an emission-reduction or
emission-limitation commitment under the Kyoto Protocol (Annex B
Party) to implement an emission-reduction project in developing
countries. Such projects can earn saleable certified emission
reduction (CER) credits, each equivalent to one tonne of CO2, which
can be counted towards meeting Kyoto targets
The mechanism stimulates sustainable development and emission
reductions, while giving industrialized countries some flexibility in
how they meet their emission reduction or limitation targets

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