Refrigerants

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 The Definition and History of Refrigerants
According to ASHRAE standard 34-1978, Refrigerant is defined as the medium of heat transfer
in a refrigerating system which picks up heat by evaporating at low temperature and pressure
and gives up heat on condensing at higher temperature and pressure.

Many of the refrigerants used during the early periods did not survive, mainly due to their
toxicity. Ammonia, however, continues to be a refrigerant of choice for food freezing
applications even today in spite of its toxicity, mainly due to its excellent thermodynamic and
thermal properties.

Carbon dioxide used in the early days of refrigeration is again being considered as a
refrigerant in spite of its high operating pressures.

Hydrocarbons used in the early part of the last century were quickly discontinued because of
their flammability. However, hydrocarbons have made a successful comeback and are being
used extensively in small domestic refrigerators and freezers in recent years.
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 The Definition and History of Refrigerants
The discovery of CFCs in the late twenties revolutionized the refrigeration industry.

Both CFCs and hydrochlorofluorocarbons (HCFCs) are non-toxic, possess excellent thermodynamic
properties, and are non-flammable.

Both CFCs and HCFCs dominated the refrigeration industry for nearly 70 years till the Montreal
Protocol imposed a ban due to their contribution to ozone depletion.

In the last two decades, hydrofluorocarbons (HFCs), which possess zero Ozone Depletion Potential
(ODP), have gradually replaced CFCs.

Very recently, global warming due to emission of various gases into the atmosphere has been the
issue being dealt with by the Kyoto Protocol HFCs which have high Global Warming Potential
(GWP) are also being banned in spite of the fact that they are ozone friendly.

Hydrofluorooelifins (HFOs), which have very low GWP and invented very recently are expected to
replace HFCs in many applications.
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Refrigerants from Different Chemical Group

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 Ammonia and the Hydrocarbons
These fluids have virtually zero ODP and zero GWP when released into the atmosphere and therefore
present a very friendly environmental picture.

Ammonia has long been used as a refrigerant for industrial applications.

The engineering and servicing requirements are well established to deal with its high toxicity and
flammability.

Ammonia cannot be used with copper or copper alloys, so refrigerant piping and components have to be
steel or aluminum.

This may present difficulties for the air conditioning market where copper has been the base material for
piping and plant.

One property that is unique to ammonia compared to all other refrigerants is that it is less dense than air,
so a leakage of ammonia results in it rising above the plant room and into the atmosphere. If the plant
room is outside or on the roof of a building, the escaping ammonia will drift away from the refrigeration
plant. 6
 Ammonia and the Hydrocarbons
The safety aspects of ammonia plants are well documented and there is reason to expect an increase in
the use of ammonia as a refrigerant.

Hydrocarbons such as propane and butane are being successfully used as replacement and new
refrigerants for R12 systems. They obviously have flammable characteristics which have to be taken
into account by health and safety requirements. However, there is a market for their use in sealed
refrigerant systems such as domestic refrigeration and unitary air-conditioners.

The newly developed refrigerant gases also have a global warming potential if released into the
atmosphere. For example, R134a has a GWP of 1300, which means that the emission of 1 kg of R134a
is equivalent to 1300 kg of CO2. The choice of refrigerant affects the GWP of the plant, but other
factors also contribute to the overall GWP and this has been represented by the term Total Equivalent
Warming Impact (TEWI). This term shows the overall impact on the global warming effect, and
includes refrigerant leakage, refrigerant recovery losses and energy consumption. It is a term which
should be calculated for each refrigeration plant. Other newly developed refrigerants include R404a
HFC R407c HFC R410a HFC R411b HCFC R717 ammonia R290 propane R600a isobutene
R1270 propylene
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 Refrigerant Blends
Many of the new, alternative refrigerants are ‘blends’, which have two or three components, developed
for existing and new plants as comparable alternatives to the refrigerants being replaced. They are
‘zeotropes’ with varying evaporating or condensing temperatures in the latent heat of vaporization
phase, referred to as the ‘temperature glide’ improving plant performance, by correct design of the heat
exchangers.

Blends or mixtures are used either to obtain different desired properties such as bubble point
temperature, oil solubility, flammability, as drop-in-substitutes for older refrigerants that are no longer
produced, etc. by combining different fluids or to obtain variable temperature refrigeration. The
mixtures used in refrigeration systems can be divided into four categories, namely, azeotropes, near-
azeotropes, zeotropes and very wide boiling zeotropes.

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Chloroflurocarbons (CFC)
These are fully halogenated fluids that have high ODP and were found to be the most responsible for the
creation of ozone hole. Use of formerly popular CFCs such as R12 and R11 in ne equipment was banned
by the Montreal Protocol. While R12 recovered from old systems may still be available, new lots of
CFCs are no longer being produced.

Hydrochlorofluorocarbons (HCFC)
Unlike fully-halogenated CFCs, which contain only carbon and halogen atoms, in the case of partially-
halogenated HCFCs, not all hydrogen atoms are replaced by halogen atoms. The remaining hydrogen
atoms facilitate partial breakdown of the compounds in the troposphere. For this reason these compounds
are less harmful to the stratospheric ozone layer, though they still have the some potential to damage the
ozone layer. However, since they are known to cause global warming, HCFCs are no longer used in the
industrialized countries of the West. Phase-out of HCFCs (mainly HCFC22, which is still widely used in
India) is being accelerated.

Hydrofluorocarbons (HFC)
Hydrofluorocarbons contain fluorine but no chlorine or bromine in the molecule, so that their ODP is
zero. Some examples of HFCs are R23, R32, R125, 134a, 143a and 152a. A problem with HFCs is that
they are chemically stable and can accumulate in the atmosphere contributing to the global warming.
Hence, HFCs need to be eventually replaced.

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Hydrofluorooelifins (HFO)
These also belong to a class of HFCs, but are derived from unsaturated hydrocarbon molecules such as propylene. HFOs are relatively
unstable, have a small atmospheric lifetime and therefore a small GWP. R1234yf and R1234ze are two HFO refrigerants invented
recently. R1234yf has been widely accepted for use in cars by the automobile industry because of its very low GWP of 4. As soon as it
becomes commercially available, R1234yf is expected to replace R134a, which is currently being widely used in air-conditioning
plants, automobile air conditioners, domestic refrigerators, etc. There are also attempts to find mixtures of R1234yf and other HFCs
such as R32 for use in other applications such as domestic air conditioners since mixtures containing R1234yf will have low GWP,
typically less than 1000.

Fluoroiodocarbons (FIC)
These are a group of chemicals containing fluorine, iodine and carbon such as, trifluoromethyl iodide (CF3I) perfluoroethyliodide
(C2F5I) and perfluoropropyl iodide (C3F7I). The FICs are reported to have zero ODP and negligible GWP due to their very short life
periods. These can also be used in blends. A blend of C3F7 and HFC 152a (51/49 mole percent) was run in a refrigerator without oil
change for over 1,500 hours without apparent ill effects. Measurements showed that the energy efficiency and capacity were equal to or
slightly better than CFC 12.

Hydrocarbons
Several hydrocarbons have excellent thermodynamic properties and can be used as refrigerants. Though alkanes, ketones, alcohols and
ethers can be used, alkanes are the most preferred group. As already mentioned, the main concern is that most of the hydrocarbons are
flammable. Here, one should note that in certain industrial applications hydrocarbons have been used as refrigerants since the beginning
of the 20th century. Hydrocarbons, for instance, are used in pure or mixture forms as refrigerants in petrochemical plants and in gas
liquefaction plants. In LNG plants, mixtures of methane and n-pentane are in common use. With adequate safety precautions
flammability will not pose a major problem in the usage of hydrocarbons. Home refrigerators have been sold in tens of millions
worldwide, including India, during the last twenty years. The ODP of hydrocarbons is zero, while their GWP is very small.
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Natural Inorganic Fluids
Ammonia is an environmentally safe but toxic working fluid which is attracting renewed attention. It possesses the most
advantageous thermodynamic and thermo-physical properties needed for refrigeration. Ammonia-based compression systems, mainly
for low temperature applications, are well developed.
These are generally suited for industrial surroundings where sufficient knowledge and facilities exist to handle chemical leaks. There
are proposals to extend its use into areas occupied by common public (e.g., comfort air conditioning, cooling of display cases in food
shops, heat pumps, etc.). But this requires careful planning and design to avoid panic and accidents in case of leaks.

Water has many desirable characteristics for cooling applications such as: thermal and chemical stability, neither toxic nor flammable,
high COP and high heat transfer coefficients. Disadvantages of water include sub-atmospheric pressure operation, large specific
compressor displacement, limitations of evaporation temperatures above 0°C and problems of lubrication.

Air has been used commercially for aircraft cooling since a long time. In spite of the low COP, this is being used because of the
operating conditions (e.g., availability of compressed air and ram effect) and stringent specifications (e.g., low weight, small size,
absolute safety, zero toxicity, etc.) which are exclusive to aircrafts. In the light of the new situation created due to the ban on synthetic
refrigerants, possible use of air for on-ground applications is being considered actively. It should be noted here that the technology
with air as refrigerant will be totally different from that with other working fluids due to the fact that air does not undergo phase
change (condensation/evaporation) at the temperature levels encountered in conventional refrigeration applications.

Use of carbon dioxide as refrigerant dates back to the early years of refrigeration. It is environmentally benign. Being the by- product
of many energy conversion processes, it is cheap and easily available. Its use as a refrigerant can reduce its release to the atmosphere,
thereby making a positive contribution to the environment. Very high operating pressure is a drawback. Because of its low critical
point, most of the thermodynamic cycle operates in the single phase region. Since CO2 enters the expansion valve as a superheated
vapour, it results in a large energy loss during the throttling process. Carbon dioxide is an excellent refrigerant when both heating and
cooling are desired. Also, it is not preferable for use in tropical countries such as India due to the high ambient temperatures11which
result in high condensing pressures.
Comparison of Different Refrigerants

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

The type of refrigerant selected for a given application depend very much on:
• The System Design,
• Size,
• Initial and Operating Costs,
• Safety,
• Reliability,
• Serviceability etc..

Due to several environmental issues such as ozone layer depletion and global warming and their relation to the
various refrigerants used, the selection of suitable refrigerant has become one of the most important issues in
recent times.

In principle, any fluid can be used as a refrigerant.

Air used in an air cycle refrigeration system can also be considered as a refrigerant.

Our attention is mainly focused on those fluids that can be used as refrigerants in vapour compression
refrigeration systems only.

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 Primary and secondary refrigerants
Primary refrigerants are those fluids, which are used directly as working fluids
• These fluids provide refrigeration by undergoing a phase change process in the evaporator

Secondary refrigerants are those liquids, which are used for transporting thermal energy
from one location to other.

• Secondary refrigerants are also known under the name brines or antifreezes.

• 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.

• Generally, the freezing point of a brine will be lower than the freezing point of its constituents.
The temperature at which freezing of a brine takes place its depends on its concentration.

• The commonly used secondary refrigerants are the solutions of water and ethylene glycol,
propylene glycol or calcium chloride. 14
 Refrigerant selection criteria
Selection of refrigerant for a particular application is based on the following
requirements:

i. Thermodynamic and thermo-physical properties

ii. Environmental and safety properties,

iii. Economics

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 Refrigerant selection criteria
Thermodynamic and thermo-physical properties:
The requirements are:
a) 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
b) 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.
c) Pressure ratio: Should be as small as possible for high volumetric efficiency and low power consumption
d) Isentropic index of compression: Should be as small as possible so that the temperature rise during
compression will be small
e) Liquid specific heat: Should be small so that degree of subcooling will be large leading to smaller amount
of flash gas at evaporator inlet
f) Vapor specific heat: Should be large so that the degree of superheating will be small
g) Thermal conductivity: Thermal conductivity in both liquid as well as vapour phase should be high for
higher heat transfer coefficients
h) Viscosity: Viscosity should be small in both liquid and vapour phases for smaller frictional pressure drops
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 Refrigerant selection criteria
Thermodynamic and thermo-physical properties:
The requirements are:
i) Latent heat of vaporization: Should be as large as possible so that the required mass flow rate per unit cooling
capacity will be small

In the above equation, Pc and Pe are the condenser and evaporator pressures, Tc and Te are condenser and
evaporator temperatures.

From the above equation, it can be seen that for given condenser and evaporator temperatures as the latent
heat of vaporization increases, the pressure ratio also increases.

Hence a trade-off is required between the latent heat of vaporization and pressure ratio.

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 Refrigerant selection criteria
Environmental and safety properties:
a) 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.

b) 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.

c) 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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 Refrigerant selection criteria
Environmental and safety properties:
d) 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. Some fluids
are toxic even in small concentrations. Some fluids are mildly toxic, i.e., they are dangerous only when
the concentration is large and duration of exposure is long. Some refrigerants such as CFCs and HCFCs
are non-toxic when mixed with air in normal condition. However, when they come in contact with an
open flame or an electrical heating element, they decompose forming highly toxic elements (e.g.
phosgene-COCl2).

In general the degree of hazard depends on:

- Amount of refrigerant used vs total space
- Type of occupancy
- Presence of open flames
- Odor of refrigerant, and
- Maintenance condition
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 Refrigerant selection criteria
Environmental and safety properties:
e) Flammability:
• The refrigerants should preferably be non-flammable and non-explosive.

• For flammable refrigerants special precautions should be taken to avoid accidents.

• Based on the above criteria, ASHRAE has divided refrigerants into six safety groups (A1 to
A3 and B1 to B3).

• Refrigerants belonging to Group A1 (e.g. R11, R12, R22, R134a, R744, R718) are least
hazardous, while refrigerants belonging to Group B3 (e.g. R1140) are most hazardous.

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

g) Compatibility with common materials of construction (both metals and non-metals) 20

 Refrigerant selection criteria
Environmental and safety properties:
h) 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

i) Dilelectric strength: This is an important property for systems using hermetic compressors.
For these systems the refrigerants should have as high a dielectric strength as possible

j) 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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 Refrigerant selection criteria
Economic properties:
The refrigerant used should preferably be inexpensive and easily available.

• No single working fluid has all these properties and a great many
different chemicals have been used over the years.

• The present situation has been dominated by the need for fluids which
are environmentally friendly.

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 Designation 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 followed by a unique number. 23
 Designation of refrigerants:
i) Fully saturated, halogenated compounds:
These refrigerants are derivatives of alkanes (CnH2n+2) such as methane (CH4), ethane (C2H6). These
refrigerants are designated by R XYZ, where:
X+1 indicates the number of Carbon (C) atoms
Y-1 indicates number of Hydrogen (H) atoms,
Z indicates number of Fluorine (F) atoms
The balance indicates the number of Chlorine atoms.
Only 2 digits indicates that the value of X is zero
Ex: R 22
X = 0 ⇒ No. of Carbon atoms = 0+1 = 1 ⇒ derivative of methane (CH4)
Y = 2 ⇒ No. of Hydrogen atoms = 2-1 = 1
Z = 2 ⇒ No. of Fluorine atoms = 2
The balance = 4 – no. of (H+F) atoms = 4-1-2 = 1 ⇒ No. of Chlorine atoms = 1
∴The chemical formula of R 22 = CHClF2
(letter a stands for isomer, e.g. molecules having same chemical
composition but different atomic arrangement, e.g. R134 and
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R134a)
 Designation of refrigerants:
ii) 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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 Designation of refrigerants:
iii) Mixtures:
Azeotropic mixtures are designated by 500 series, where as zeotropic refrigerants (e.g. non-
azeotropic mixtures) are designated by 400 series.

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 Designation of refrigerants:
iv) Hydrocarbons:

Propane (C3H8) : R 290

n-butane (C4H10) : R 600

iso-butane (C4H10) : R 600a

Unsaturated Hydrocarbons: R1150 (C2H4)

R1270 (C3H6)

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 Conclusion
Thus, there are no refrigerants in the horizon that completely meet the safety, stability, energy
efficiency and environmental friendliness.
It seems that the refrigeration industry will have very little choice but to use flammable
refrigerants (HFOs, low GWP HFCs, HCs, NH3, etc).

Since the energy efficiency of HFOs is somewhat low, mixtures of medium GWP fluids such
as R32 and low GWP refrigerants such as R1234yf may be the working fluids of choice in the
immediate future.
Meanwhile, the quest for better molecules continues. Barring new inventions, natural
refrigerants appear to be the best choice in the long term.

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