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Accepted Manuscript
International Journal of Air-Conditioning and Refrigeration
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Article Title: Recent development in search for alternative low global warming potential
refrigerants: A review

Author(s): M. U. Siddiqui, Amro Owes, F. G. Alamri, Farooq Saeed

DOI: 10.1142/S2010132520300049

Received: 01 April 2020

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Accepted: 06 July 2020

To be cited as: M. U. Siddiqui et al., Recent development in search for alternative low
global warming potential refrigerants: A review, International Journal of
Air-Conditioning and Refrigeration, doi: 10.1142/S2010132520300049

Link to final version: https://doi.org/10.1142/S2010132520300049

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Recent development in search for alternative low global warming

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potential refrigerants: A review
M. U. Siddiqui, Amro Owes*, F. G. Alamri, Farooq Saeed
Mechanical and Energy Engineering Department, Imam Abdulrahman Bin Faisal University, Kingdom of
Saudi Arabia
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Structure:-
Abstract
1. Introduction
2. Progressive development of refrigerants
3. Search for alternative refrigerants
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a. Alternative refrigerants for R12

b. Alternative refrigerants for R22
c. Alternative refrigerants for R507A
d. Alternative refrigerants for R404A
e. Alternative refrigerants for R410A
f. Alternative refrigerants for R134A
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g. Alternative refrigerants for R245fa

h. Prospects of using Natural Refrigerants as alternative refrigerants

4. Safety Impact review

5. Conclusions and Recommendations
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References
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Abstract
Conventionally CFC type refrigerants were used until Montreal Protocol which stated that CFC

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refrigerants cause ozone depletion and should be replaced with alternative refrigerants. The
alternative refrigerants are safe for ozone but they have comparatively high flammability, toxicity
and global warming potential. Thus they need careful handling. In Koyoto Protocol, it was stated
that the currently used refrigerants with high global warming potential needs to be replaced with
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yet other alternative refrigerants with low global warming potential. This paper comprehensively

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reviews those recent studies that focused over the possible replacement of currently in-use
refrigerant with a comparatively more environment-friendly alternative refrigerant. Initially the
progression of refrigerants through different generations has been described and discussed. A
list of currently in-use refrigerants has been presented. Then, the scientific development for the

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replacement of listed refrigerants are thoroughly reviewed and critically analyzed. From the
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comprehensive review, it was found that R1234yf has the most potential to be a suitable low-
flammable replacement for R134a for domestic refrigeration and automotive air-conditioning
systems. Also, R32 has the most potential to be a suitable alternative of R410A.
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Keywords
Low GWP refrigerants; environment friendly refrigerants; Alternatives for R22; Alternatives for
R134A; Alternatives for R410A;
1. Introduction
Refrigeration and Air-conditioning systems commercially used on a household or industrial
scale are mostly compression type units. These units utilizes a refrigeration cycle that
comprises of components i.e. compressor, condenser, expander and evaporator. The working
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fluid within these units is known as refrigerant. The design of any refrigeration or air-conditioning
system largely depends upon the selection of refrigerant to be used in the refrigeration cycle.
Thus the properties of refrigerants are quite significant and play a vital role in the utilization of
refrigeration and air-conditioning units.
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On a larger scale, the properties of these refrigerants could be characterized as

performance properties, environmental, health and safety properties. Most of the thermo-
physical properties involving boiling temperature of refrigerant, latent heat of condensation and
vaporization, molecular mass, density, critical temperature, critical pressure, etc. These
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properties directly affect the performance of any refrigeration system and thus help in the
designing and performance assessment of the refrigerating system.

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Beside Performance properties, there are some other properties of the refrigerants that
affect the environment and their interaction with the surrounding. These are known as
Environment, health and safety properties. The most significant environment, health and safety
properties of refrigerants are as follows:-
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a) Ozone Depletion Potential (ODP).
b) Global Warming Potential (GWP)
c) Flammability
d) Toxicity

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Ozone Depletion Potential (ODP) is a property of the refrigerant which effects the
environment by depleting Ozone layer. They diffuse up into the stratosphere where ultraviolent
radiation from the sun discharges their chlorine atoms. Chemical reactions between chlorine
atoms and ozone, in the atmosphere, result in the development of chlorine monoxide which
reacts again with ozone forming oxygen and regenerates more chlorine atoms that continue
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conversion of the ozone molecules. Thus, even a small amount of any refrigerant which
depletes ozone layer can cause a great damage to the ozone layer. It is this ozone layer which
absorbs the solar ultraviolet radiations protecting both humans and other living things from its
exposure [1]. ODP is a relative property which is measured as the refrigerant’s ability to deplete
stratospheric ozone compared to ozone depletion by R11 (where R11 is considered as a
reference with an ODP value of 1.0).
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Global Warming Potential (GWP) is a property of the refrigerant that measures the ability of
a refrigerant to collect radiant energy compared to CO2. Additional carbon dioxide which is
artificially produced by the humans as a result of burning fuel is considered as a greenhouse
gas because it develops a layer in the atmosphere and has the ability to absorb a lot of earth’s
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radiant energy thus overall increasing the global temperature thereby contributing towards
climatic change and global warming. The refrigerant’s ability to behave as a greenhouse gas is
known as Global Warming Potential. GWP is also a relative property which is measured as a
refrigerant’s ability to collect radiant energy compared to the radiant energy collection by CO2
(where CO2 R744 is considered as a reference with a GWP of 1.0).
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Flammability is a property of a mixture in which a flame is capable of self-propagating for a

certain distance. Flammability of a refrigerant is its ability to burn or ignite, causing fire or

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combustion. The safety designation of refrigerants has been classified by ASHRAE standard 34
that uses four classes (1, 2, 2L and 3) according to their Flammarion Hazards. Moreover, the
toxicity of the refrigerant which is defined as the capability of the refrigerant to poison or do
damage on the health of a person. The toxicity of refrigerants is also specified as per ASHRAE
standard 34 that uses two classes (A and B) according to their health hazards.
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Each refrigerant has its own thermo-physical properties as well as environment, health
and safety properties. Replacing a refrigerant as a result of poor environmental properties with
another alternative refrigerant will have a definite effect over the performance of the refrigeration
system. Therefore, the main objective of this paper is to investigate the development of currently
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in-use refrigerants though the different generations. Also, the search is attempting to find new
alternative refrigerants instead of the currently in-use refrigerants though the previous studies.

2. Progressive development of refrigerants

Refrigerants have been in use for more than over a century and there has been a
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systematic evolution of refrigerants during this time. For any fluid to be considered as a possible
refrigerant candidate within the refrigeration and air-conditioning systems, it should possess the
following desirable properties.
• High enthalpy of vaporization, to guarantee maximum heat absorption during
refrigeration.
• Smaller vapor density, to enable using of smaller compressors.
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• High thermal conductivity, for high heat transfer rate during evaporation and
condensation process.
• Minimum specific heat, to ensure small change in entropy in the throttling process.
• Suitable critical temperature, to ensure large range of isothermal energy transfer.
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Considering the aforementioned desirable properties of the refrigerants; Ammonia R717,

carbon dioxide CO2, Propane R290 and Isobutene R600a have been considered as the first
generation refrigerants. However, although having several desirable properties, the first
generation of refrigerants is flammable, toxic and chemically not stable. This leads to second
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generation of refrigerants [2]. The second generation of refrigerants includes

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chlorofluorocarbons (CFCs) and hydro-chlorofluorocarbons (HCFCs). These second generation

halogenated refrigerants have suitable properties as stability, nonflammable, nontoxic and

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adequate material compatibility. This led to their spread use in refrigerating and air conditioning
systems and more preferable than the first generation refrigerants. However, later it was
discovered that these refrigerants are basically harmful chemicals to the environment [3]. The
chlorine present in these second generation refrigerants is the main agent for depleting ozone in
the stratosphere.
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Due to the high ODP of second generation refrigerants, this leads to third generation of
refrigerants. The third generation of refrigerants is hydro-fluorocarbons HFCs. Although, within
the third generation of refrigerants, chlorine based refrigerants were phased out thus solving the
problem of high ODP yet, it was discovered that the HFCs are potential greenhouse gases. It
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was discovered that they can be hundreds to thousands of times more potent than carbon
dioxide (CO2) in contributing to climate change. The fluorinated refrigerants of the third
generation have significantly higher GWP and thus pose a serious threat to our climate.
Removing chlorinated and fluorinated refrigerants, we return back to basic hydrocarbons HCs
and the Natural refrigerants which do not depletes ozone and does not contribute in global
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warming but are highly flammable and toxic. At present, there is no ideal fluid in all regards [3]
and the search of new alternatives of refrigerants is still going on [4].

Nowadays, it is established that ozone depletion and global warming are presenting the
most important universal environmental problems. Several international efforts have been made
attempting to protect our environment from the effect of utilizing harmful refrigerants. The first
step in international efforts to protect stratospheric ozone was Montreal Protocol, signed in 1987
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and Koyoto Protocol signed in 1997. Montreal Protocol focused over saving the environment
against high ODP refrigerants whereas the Koyoto Protocol focused against high GWP
refrigerants.

On October 15, 2016, 197 countries adopted an amendment to phase down HFCs under
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the Montreal Protocol [5]. As per the amendment, countries committed to cut the consumption
and production of HFCs by more than 80% in the coming 30 years. As per the phase down
schedule, the developed countries should reduce HFC consumption beginning in 2019. Most
developing countries should freeze consumption in 2024, with a small number of developing
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countries with unique circumstances freezing consumption in 2028.

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3. Search for Alternative Refrigerants

The need of refrigeration in day-to-day life of a civilized society is well established,

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however, researchers are still in search of refrigerants which could provide all of the desirable
thermo-physical properties with low level of flammability, toxicity, ODP and GWP. After the
passing of Montreal Protocol, the use of second generation refrigerants was severely
constrained and the third generation refrigerants i.e. R507A, R404A, R410A, R134a, R245fa
etc., were focused for the production and consumption in various sectors of refrigeration and air-
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conditioning [6]. The choice of refrigerant severely affects the design of the refrigeration
equipment. The thermo-physical properties of the refrigerant are the reason for defining the size
of different component of the refrigeration equipment. As a result, currently throughout the world
most of the refrigeration equipment is designed and manufactured according to the third
generation refrigerants [7].
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Kyoto Protocol established the fact that third generation refrigerants have high GWP and
use of these are also harmful for the environment. This leads to an economic dilemma as most
of the manufactured and in-use refrigeration equipment is designed for third generation
refrigerant thus making it impractical to replace all of the available refrigeration equipment. So
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the researchers came with the idea of “drop-in” and “retrofit” refrigerants.
a) Drop-in refrigerants are considered those alternative refrigerants which can be
directly used in the refrigeration equipment pre-designed without the need for any
modification within the equipment itself.
b) Retrofitting refrigerants are considered those alternative refrigerants which cannot be
directly used in the refrigeration equipment pre-designed, however minor
modification within this equipment could make it suitable to be used within this
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equipment.

The thermo-physical properties of refrigerants are the key parameters which determine the
behavior of any refrigeration equipment operating with a drop-in or retrofitted refrigerant. Calm &
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Hourahan [8] reported the thermo-physical properties of the refrigerants while they later updated
[9]. However so far, the most recent and updated thermo-physical properties data has been
collected by UNEP report 2014 [10]. Due to the interest of the global environment caused by
high global warming potential of refrigerants, the properties of refrigerants received more
attention such as: [11], [12], [13], [14], and [15].
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In 2009, Mohanraj et al. [16] offered a review article for various theoretical and
experimental investigations carried out with low GWP alternatives, since then, significant

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amount of new investigations have been carried out. As a contemporary issue, the changing of
a retrofit refrigerant arises an essential problem in the operation of the compressor because of
the change of lubricity of oil with the refrigerant [17]. Therefore, oil-free linear compressors have
been investigated for operating refrigeration equipment [18]. Recently halogenated olefins have
also been investigated as a replacement of some currently widely used refrigerants [19].
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i) Alternative Refrigerants for R12
R12 is one of the early refrigerants that belong to second generation of refrigerants. For
most part, it has been well understood as a highly harmful refrigerant to the environment. The

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harmful effects are a result of its high ODP and GWP i.e. ODP of 0.73 and a GWP of 10300.
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However, due to its non-flammability, non-toxicity and excellent thermo-physical properties, it

was widely used in refrigeration equipment as well as air-conditioning chillers. In search of its
replacement, Mani & Selladurai [20] found that a mixture of R290/R600a (68/32 by weight
percentage) could turn out to be a drop-in replacement for R12. Kumar and Rajagopal [21]
considered the R123 & R290 as possible replacement for R12. Their investigation results
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indicated that R123 alone is not a suitable replacement due to its high specific volume at suction
and high boiling point, however a mixture of R123/R290 (70%/30%) would turn out to be a
suitable replacement for R12. Dalkilic and Wongwises [22] theoretically analyzed several
refrigerants for the replacement of R12. The results of their analysis indicated that a mixture of
R290/R600a (40/60 by weight percentage) turns out to be suitable replacement for R12.

ii) Alternative Refrigerants for R22

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R22 was originally used for low-temperature applications and later air-conditioning, and
is today one of the most popular HCFC refrigerant. It is classified as an A1 refrigerant and is the
widely used refrigerant in the world for industrial processes, commercial refrigeration, and
mainly air-to-air cooling systems [23, 24]. It has an ODP value of 0.034 which is less than R12
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and a GWP of 1780. Due to its ozone depletion potential and high GWP, a number of
researches have been carried out to find its most suitable replacement. R422A, R417B and
R404A were experimentally analyzed [25, 26] for the possibility of drop-in replacement for R22.
The results indicated that there is a significant drop in the COP of the system however R417B
turn out to be the most suitable substitute. Antunes and Filho [27] experimentally analyzed the
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possibility of drop-in replacement of R22 with R438A, R404A, R410A, R32, R290 and R1270.
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Their results indicated that R404A is the least suitable replacement whereas R290 & R1270 are
most candidates for replacement of R22. Messineo et al. [28] investigated the possibility of

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replacement of R22 with R417A, R407C and R404A; however their results indicated a
significant decrease in the performance when compared to R22. Panato et al. [29]
experimentally analyzed the possibility of drop-in replacement of R22 with R1270, R438A,
R404A and R134A. Their results indicated that the R438A was the most flexible substitute for
replacement of R22, whereas R1270 had the highest cooling capacity value.
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Fannou et al. [30] concluded that R407C is a much better substitute for retrofitting R22
as compared to R410A for a direct expansion geothermal evaporator. Elgendy and Fatouh [31]
showed that R438A could be used as a retrofit refrigerant for R22 with approximately 11%
decrease in the COP. Dalkilic and Wongwises [22] theoretically analyzed several refrigerants for
the replacement of R22. The results of their analysis indicated that a mixture of R290/R1270
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(20/80 by weight percentage) turns out to be suitable replacement for R22. Devecioʇlu and Oruç
[32] tested N20 and R444B refrigerants as alternatives for R22. Their results indicated that
R444B is the better option among the tested refrigerants. Joudi and Al-Amir [33] experimentally
investigated the possibility of replacing R22 with R290, R407C and R410A for residential air-
conditioning systems at high ambient temperatures. They concluded that R290 is a better
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candidate among others for operation at high ambient temperatures whereas the R407C has
performance very close to R22. Choudhari and Sapali [34] also suggested that R290 is a much
better substitute for R22 refrigerant. Padalkar et al. [35] also suggested R290 as a substitute for
R22 in split packaged air-conditioner. Teng et al. [36] reported that 50-55% is the optimal mass
for charging the window air-conditioner with R290 while retrofitting it as a replacement for R22.
Rocca and Panno [37] tested experimentally the possibility of using R417A, R422A and
R422D as drop-in substitutes for R22. Although they reported that none of their tested
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substitutes performed satisfactory yet R417A resulted in much better performance compared to
the other substitutes. Vandaarkuzhali [38] discussed in details the pros and cons of replacing
R22 with R152a in commercial air conditioning systems. Sethi et al. [39] studied the possible
replacement of R22 with R407C & R444B refrigerants for air-conditioning at high ambient
temperatures. The results of their analysis indicated that R444B is a much better substitute for
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R22 when compared with R407C at high ambient temperatures. Subiantoro et al. [40] studied
several substitutes for R22. They reported that while R744 is most environment friendly
refrigerant, R290 & R407C are most suitable for retrofitting application whereas R290 & R134a
have much better performance compared to the others.
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Bolaji et al. [41] thermodynamically studied the possibility of replacing R22 with R429A,
R435A & R457A substitutes. The results of their analysis indicated that all of the tested

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refrigerants performed better than R22 with lower pressure ratios and discharge pressure than
R22. R435A is found to have much better performance compared to others. Similar result has
been reported by Devecioğlu and Oruç [42] suggesting R453A as a possible replacement for
R22. Same authors [43] also reported that R424A is a much better substitute for R22 when
compared with R417A. Figure 1 summarizes the potential alternatives reported in literature as a
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replacement for R22. The safety and environmental data for these alternative refrigerants are
reported in Table 1. “Low COP” corresponds to low COP of alternative compared to R22 as
reported in literature whereas “High GWP” corresponds to a comparatively higher GWP value
when compared with GWP of all tested alternatives. For R22, a GWP value higher than 400 for
the alternative refrigerant is considered as “High GWP”.
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Figure 1 – Summary of the alternatives for R22 as reported in literature.

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Table (1) Thermo-physical properties, safety and environmental data for alternative refrigerants
of R22 [148, 150 and 151]

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Boiling Critical Critical
Safety *
Refrigerant Formula Point Temperature Pressure ODP GWP100
Group
(˚C) (˚C) (kPa )
Chlorodifluoromethane
R22 CHClF2
–41 96.145 4990.0 A1 0.034 1760
Difluoromethane
R32 CH2F2
–52 78.105 5782.0 A2L 0.00 677
1,1,1,2-Tetrafluoroethane
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R134A –26 72.707 3761.0 A1 0.00 4800

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CH2FCF3
1,1-Difluoroethane
R152A CH3CHF2
–24 113.26 4516.8 A2 0.00 138
Propane
R290 C3H8
–42 96.74 4251.2 A3 0.00 5
Unsaturated Organic Compounds
2,3,3,3-tetrafluoro-1 propene
R1234yf CF3CF=CH2
–29.4 94.7 3382.2 A2L 0.00 <1
Propylene
R1270
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C3H6
Zeotropic Blends (% by mass)
R-125/143a/134a
R404A (44/52/4)
–46.6 72.046 3728.9 A1 0.00 3940
R-32/125/134a
R407C (23/25/52)
–43.8 86.034 4629.8 A1 0.00 1620
R-32/125
R410A (50/50)
–51.6 71.358 4902.6 A1 0.00 1920
R-125/134a/600
R417A –38.0 87.1 4039 A1 0.00 2130
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(46.6/50.0/3.4)
R-125/134a/600
R417B (79.0/18.3/2.7)
–44.9 75.219 3831.59 A1 0.00 2740
R-125/134a/600a
R422A (85.1/11.5/3.4)
–46.5 71.7 3750 A1 0.00 2850
R-125/134a/600a
R422D (65.1/31.5/3.4)
–43.2 79.6 3905 A1 0.00 2470
R125/134a/600a/600/601a
R424A (50.5/47.0/0.9/1.0/0.6)
–39.1 88.8 4040 A1 0.00 2210
R-E170/152a/600a
R429A (60.0/10.0/30.0)
–26.0 127.04 5173.15 A3 0.00 20
R-E170/152a
R435A (80.0/20.0)
–26.1 125.087 5385.17 A3 0.00 28
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R-32/125/134a/600/601a
R438A (8.5/45.0/44.2/1.7/0.6)
–43.0 83.74 4216 A1 0.00 2060
R-32/152a/1234ze(E)
R444B (41.5/10.0/48.5)
–44.6 92.11 5212.21 A2L 0.00 295
R32/125/134a/227ea/600/601
R453A a –42.2 87.9 4530 A1 0.00 1640
(20.0/20.0/53.8/5.0/0.6/0.6)
R-32/1234yf/152a
R457A –42.7 98.65 3950 A2L 0.00 139
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(18.0/70.0/12.0)
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)

iii) Alternative Refrigerants for R507A

R507A is another refrigerant which is widely used in commercial refrigeration systems.
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With an acceptable efficiency, it is classified as A1 category refrigerant. One of the major

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advantages of this refrigerant is the low discharge temperature which makes it possible to
achieve high temperature lift in a single stage system. Therefore it is also used for industrial

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refrigeration. Although this refrigerant does not deplete ozone however it has a high GWP of
about 4300 which makes it viable to be replaced. Vaitkus and Dagilis [44] theoretically analyzed
the possible alternatives of R507A and R404A for eutectic refrigeration systems. Their analysis
indicated a decrease in refrigeration capacity when using R407F, R407A, R448A and R449A
drop-in refrigerants with R448A demonstrating a significant decrease in refrigerating capacity
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when used as a drop-in for R507A refrigerant. Llopis et al. [45] experimentally tested the
possible replacement of R507A with R513A & R450A for medium temperature commercial
refrigeration systems. Their experimental results indicated that both R513A & R450A could be
used as a replacement for R507A with R513A demonstrating better results. Figure 2
summarizes the potential alternatives reported in literature as a replacement for R507A. “Low
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COP” corresponds to low COP of alternative compared to R507A as reported in literature

whereas “High GWP” corresponds to a comparatively higher GWP value when compared with
GWP of all tested alternatives. For R507A, a GWP value higher than 600 for the alternative
refrigerant is considered as “High GWP”. The safety and environmental data of alternative
refrigerants for R507A are presented in Table 2.
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Figure 2 – Summary of the alternatives for R507A as reported in literature.

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Table (2) Thermo-physical properties, safety and environmental data for alternative refrigerants
of R507A [148, 150 and 151]

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Boiling Critical Critical
Safety *
Refrigerant Formula Point Temperature Pressure ODP GWP100
Group
(˚C) (˚C) (kPa )
Azeotropic Blends (% by mass)
R507A R125/143a (50.0/50.0) –46.7 70.62 3705 A1 0.00 3990
R513A R1234yf/134a (56.0/44.0) –29.1 96.5 3767 A1 0.00 573
Zeotropic Blends (% by mass)
R407A R32/125/134a (20.0/40.0/40.0) –45.2 82.3 4515 A1 0.00 1920
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R407F R32/125/134a (30.0/30.0/40.0) –46.1 82.7 4750 A1 0.00 1670
R32/125/1234yf/134a/1234ze(E)
R448A (26.0/26.0/20.0/21.0/7.0)
–45.9 83.7 4660 A1 0.00 1360
R32/125/1234yf/134a
R449A (24.3/24.7/25.3/25.7)
–46.0 83.87 4387.5 A1 0.00 1280
R450A R134a/1234ze(E) (42.0/58.0) –23.4 104.4 3820 A1 0.00 547
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)

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iv) Alternative Refrigerants for R404A

R404A is another refrigerant similar to R507A used in commercial refrigeration systems.
It is classified as A1 category refrigerant. Similar to R507A, one of the major advantages of this
refrigerant is the low discharge temperature which makes it possible to achieve high
temperature lift in a single stage system. Although this refrigerant does not deplete ozone
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however it has a high GWP of about 4200 which makes it worthwhile to be replaced. Devecioʇlu
and Oruç [32] tested DR33, L40, DR7 and R448A refrigerants as alternatives for R404A. Their
results indicated that L40 is the better option among the tested refrigerants. Mota-Babiloni et al.
[46] reported that N40, L40 and DR7 are possible alternatives for R404A with N40 showing
most promising results. Mendoza-Miranda et al. [47] showed that R450A and R404A provide a
much better fit for shell and micro fin tube evaporator model. Experimentally R448A has also
been tested for substituting R404A in refrigeration systems [48]. Along with that, experiments
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have also been reported that shows R410A to be a feasible substitute for R404A in Medium
Temperature Refrigeration Systems whereas R407F to be a feasible substitute for R404A in
Low Temperature Refrigeration Systems [49]. Mota-Babiloni et al. [50] showed experimentally
that L40 and DR7 are the most suitable low flammable alternates to R404A whereas N40 and
DR33 are the most suitable alternates if no flammability is acceptable. Oruç et al. [51] showed
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that both R442A & R453A improve the performance of an R404A system with R453A showing
much better improvement. Figure 3 summarizes the potential alternatives reported in literature
as a replacement for R404A. “Low COP” corresponds to low COP of alternative compared to
R404A as reported in literature whereas “High GWP” corresponds to a comparatively higher
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GWP value when compared with GWP of all tested alternatives. For R404A, a GWP value
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higher than 1300 for the alternative refrigerant is considered as “High GWP”. The safety and
environmental data of alternative refrigerants for R404A are presented in Table 3.

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Figure 3 – Summary of the alternatives for R404A as reported in literature.

Table (3) Thermo-physical properties, safety and environmental data for alternative refrigerants
of R404A [148, 149 and 151]
Critical
TE

Boiling Critical
Refrigeran Temperatu Safety *
Formula Point Pressure ODP GWP100
t re Group
(˚C) (kPa )
(˚C)
Zeotropic Blends (% by mass)
R404A R-125/143a/134a (44/52/4) –46.6 72.046 3728.9 A1 0.00 3940
R407A R32/125/134a(20.0/40.0/40.0) –45.2 82.3 4515 A1 0.00 1920
R407F R32/125/134a(30.0/30.0/40.0) –46.1 82.7 4750 A1 0.00 1670
R410A –51.6 71.4 4902.6 A1 0.00 1920
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R-32/125 (50/50)
R-32/125/134a/152a/227ea
R442A (31.0/31.0/30.0/3.0/5.0)
–46.5 82.4 4760 A1 0.00 1750
N40 R32/125/1234yf/134a/1234ze(E)
(26.0/26.0/20.0/21.0/7.0)
–45.9 83.7 4660 A1 0.00 1360
R448A
R32/125/1234yf/134a
R449A (24.3/24.7/25.3/25.7)
–46.0 83.87 4387.5 A1 0.00 1280
R450A R134a/1234ze(E) (42.0/58.0) –23.4 104.4 3820 A1 0.00 547
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R32/125/134a/227ea/600/601a
R453A (20.0/20.0/53.8/5.0/0.6/0.6)
–42.2 87.9 4530 A1 0.00 1640
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DR7
R-32/1234yf (36/64) –48.4 89.17 4550 A2L 0.00 238
(R454A)

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DR33 R-32/125/1234yf/134a
(24.3/24.7/25.3/25.7)
–46.0 85.02 4480 A1 0.00 1280
(R449A)
L40 R-1234yf/R-32/R-744
(75.5/21.5/3%)
–52.1 85.6 4660 A2L 0.00 146
(R455A)
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)

v) Alternative Refrigerants for R410A

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R410A is another refrigerant which is widely used in chiller, air-conditioning and heat
pump systems. It is classified as A1 category refrigerant. The pressure of this refrigerant is
higher than R22 and R404A while its efficiency is very similar to R22 especially at lower
temperatures. However its efficiency declines at a much greater rate at higher ambient
temperatures. Although this refrigerant does not deplete ozone however it has a high GWP of

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about 2100 which makes it worthwhile to be replaced. Mota-Babiloni et al. [46] reported that L41
and DR5 are possible alternatives for R410A with DR5 showing most promising results.
Devecioʇlu and Oruç [32] tested DR5 and R447A refrigerants as alternatives for R410A. Their
results also indicated that DR5 is the better option among the tested refrigerants.
Tian et al. [52] theoretically and experimentally investigated the possibility of using a
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mixture of R32/R290 (68/32 by weight percentage) as a drop-in replacement for R410A in

household air-conditioners. They reported that, with a very low GWP, this mixture could actually
have a much better performance than R410A alone with a reduced charge amount and increase
cooling capacity. Han et al. [53] theoretically and experimentally proved that R161 is a much
better alternative to be used in replacement of R410A as well as R32. The results were reported
for a small scale refrigeration system which showed that R161 can achieve higher COP with a
discharging temperature much lower than R410A. Yao et al. [54] considered R32 as a drop-in
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replacement for R410A for direct evaporative fresh air handling equipment in industry,
commerce and similar purposes. They reported that R32 can sustain performance however
need reconsideration when operating at high temperature above 35°C.
Creamaschi et al. [55] focused over the performance of the compressor in residential
and commercial air conditioning equipment when replacing R410A with R32 or R1234yf
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refrigerants. The results of their analysis indicated that R32 have the highest discharge
temperature. Longo et al. [56] studied the experimental heat transfer coefficients and pressure
drop inside a commercial brazed plate heat exchanger when replacing R410A with R32. The
heat transfer coefficient was significantly higher with a slightly higher pressure drop rendering
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R32 as a promising low GWP substitute for R410A refrigerant in medium size heat pumps and
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chillers. Botticella et al. [57] studied the performance of a 5kW residential space heating split
system by replacing common refrigerants with several low GWP alternatives. The results of their

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analysis indicated that R32 have the ability of reach best energetic performance with a fixed set-
up cost as replacement for R410A.
In et al. [58] investigated the partial load performance of a residential heat pump system
when replacing R410A with R32 and R446A refrigerants. Based on optimal refrigerant charge
requirement, performance of the system and compressor input requirement, R32 turns out to be
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a better replacement for R410A system compared to R446A. In et al. [59] investigated the
possible drop-in replacement of R410A residential heat pump with R32 and L41b refrigerants.
The results of their analysis indicated that both of these substitutes have similar performance
and could be used as a replacement for R410A however L41b have slightly better performance
than R32. Devecioğlu [60] theoretically investigated the possibility of replacing R410A in heat
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pump air-conditioning devices with low GWP substitutes i.e. R446A, R447A, R452B and R454B.
It was reported that R452B is a better alternative for R410A at heating mode whereas if cooling
is needed only, then R446A showed much promising results. Alabdulkarem et al. [61]
theoretically simulated the possibility of drop-in replacement of R410A with low GWP refrigerant
i.e. R32, D2Y60 and L41a for a 10.55kW split type heat pump. The results of their analysis
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indicated that both R32 & L41a are suitable replacement for R410A refrigerant. Also, it was
reported that R410A do not offer new advantages compared to pure R32 [62]. Figure 4
summarizes the potential alternatives reported in literature as a replacement for R410A. Also,
Table 4 shows the properties, safety and environmental data for alternative refrigerants of
R410A.
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Figure 4 – Summary of the alternatives for R410A as reported in literature.

Table (4) Thermo-physical properties, safety and environmental data for alternative refrigerants
of R410A [148, 149 and 151]
Boiling Critical Critical
Safety
Refrigerant Formula Point Temperature Pressure ODP GWP100*
Group
(˚C) (˚C) (kPa )
Difluoromethane
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R32 CH2F2
–52 78.105 5782.0 A2L 0.00 677
2,3,3,3-tetrafluoro-1 propene
R1234yf CF3CF=CH2
–29.4 94.7 3382.2 A2L 0.00 <1
Fluoroethane
R 161 CH3CH2F
–37.6 102.2 5090 A3 0.00 12
Blends (% by mass)
R410A R-32/125 (50/50) –51.6 71.358 4902.6 A1 0.00 1920
DR-5 R-32/R-1234yf (72.5/27.5) –45.40 83.11 5400 A2L 0.00 <500
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D2Y60 R-32/R-1234yf (40/60) N/A N/A N/A A2L 0.00 272

R-32/R-1234yf/R-1234ze(E)
L41A (73/15/12)
N/A N/A N/A A2L 0.00 494
R-32/1234ze(E)/600
R446A (68.0/2.09/3.0)
–49.4 84.17 5634.93 A2L 0.00 461
R-32/125/1234ze(E)
R447A (68.0/3.5/28.5)
–49.3 82.62 5536.12 A2L 0.00 572
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R-32/R-125/R-1234yf
R452B (67 /7 /26)
–51.0 77.1 5220 A2L 0.00 676
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)
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vi) Alternative Refrigerants for R134A

R134A is another refrigerant which is widely used in a variety of equipment including

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chiller, mobile air-conditioning and domestic refrigeration systems. It is classified as A1 category
refrigerant. The pressure of this refrigerant is lower than R22 and similar to R12 while its
efficiency is good. Although this refrigerant does not deplete ozone however it has a high GWP
of about 1360 which makes it worthwhile to be replaced. Mota-Babiloni et al. [46] reported that
N13, XP10 and ARM42a are possible alternatives for R134A with N13 showing most promising
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results. Llopis et al. [45] experimentally tested the possible replacement of R134A with R513A &
R450A for medium temperature commercial refrigeration systems. Their experimental results
indicated that both R513A & R450A could be used as a replacement for R134A with R450A
demonstrating better results. Makhnatch et al. [63] also showed that R450A could be used as a
drop-in refrigerant for R134a in small capacity refrigeration units. Devecioʇlu and Oruç [32]
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tested R450A, R513A, R1234yf and R1234ze (E) refrigerants as alternatives for R134A. Their
results indicated that R1234yf is the better option among the tested refrigerants.
Lee et al. [64] studied the performance of a solar heat pump using R1233zd-E in place
of R134A. The result of their analysis indicated that although the heat capacity of such systems
using R1233zd-E is lower than that with R134A yet the COP is higher than R134A due to much
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lower power consumption rate. Mohanraj [65] theoretically assessed the possibility of replacing
R134A with R430A for domestic refrigerators. It was reported that R430A have similar
volumetric cooling capacity as R134A so compressor could be used without modifications.
Along with that, the COP of R430A was also found slightly higher than R134A thus proving it to
be a suitable drop-in replacement of R134A. Mota-Babiloni et al. [66] experimentally assessed
the possibility of replacing R134A with R513A concluding that R513A can replace R134A with
only a thermostatic expansion valve adjustment ensuring better performance, higher cooling
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capacity and lower discharge temperature.

Domestic refrigeration is one of the most important sectors in the refrigeration systems.
Thus it is imperative to search a low GWP refrigerant for domestic uses. Borokinni [1] performed
an experimental investigation for evaluating the possibility of replacing R134A with R510A and
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R600a refrigerants for domestic refrigerators. The results of the analysis indicated that both of
the tested refrigerants operated with higher COP than R134A with the best performance
achieved by R510A in the retrofitted system. However Rasti et al. [67] argued in favor of R600a
as a suitable alternate for R134a system when compared to R436A refrigerant. Cabello et al.
[68] tested the possibility of drop-in replacement of R134A with R152a refrigerant concluding
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that compressor is compatible with both the refrigerants and the performance of the system
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improved by 13% despite a reduction of 10% in the cooling capacity due to the replacement of
R134A with R152a. Cabello et al. [69] also reported that R152A could be used as a drop-in

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refrigerant for R134a in cascade refrigeration plants. Mota-Babiloni et al. [70] experimentally
assessed the possibility of drop-in replacement of R134A with R450A concluding that R450A
could be considered as a suitable candidate for replacing R134A since both operate at relatively
same COP although there is an approximately 6% decrease in the cooling capacity by R450A.
Automotive air-conditioning is one another important sector for utilization of refrigerants.
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Search of low GWP refrigerants in this sector is still ongoing [71]. For instance, Vaghela [72]
tested the possibility of replacing R134a within automotive air conditioners with R290, R407C,
R600a, R410A, R404A, R1234yf & R152a concluding that R1234yf is best alternative among
others for mobile air-conditioning. Devecioğlu and Oruç [73] considered the possibility of
replacing R134a with R1234yf, R444A & R445A refrigerant substitutes. They concluded that
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although R1234yf provided the best performance results yet R444A could be considered for
heavy vehicles due to its non-flammability characteristics. Daviran et al. [74] theoretically
simulated the performance of an automotive air-conditioning system by replacing R134a with
R1234yf concluding that both refrigerants have similar performance under varying conditions
making R1234yf a suitable replacement for R134a in the automotive air conditioning system.
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The second law analysis of replacing R134a with R1234yf has been reported by Golzari et al.
[75] for automotive air-conditioning system. The experimental work for this replacement is
reported by Cho and Park [76] for varying compressor speeds of automotive air-conditioning
system. Molés et al. [77] reported that an internal heat exchanger could produce significant
increment on the cooling capacity and COP of an R1234yf operated vapor compression system.
Cho et al. [78] reported that without internal heat exchanger the COP of R1234yf for automotive
air-conditioning reduced up to 4-7% whereas with an internal heat exchanger the reduction
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minimizes to 1.8-2.9% only. Similar results were also reported by Bobbo et al. [79].
Aprea et al. [80] experimentally tested the drop-in replacement of R134a with R1234yf
for domestic refrigerators reporting a slight improvement in the cooling capacity rendering it a
suitable replacement for R134a in domestic refrigerators. Similar results were also reported by
Belman-Flores et al. [81] for domestic refrigeration. Righetti et al. [82] compared the
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performance of low GWP refrigerants R1234yf, R1234ze(E) and R600a as a replacement of

R134a for household refrigerators. They reported that although all of the tested substitutes
could be considered as good replacements yet only R1234yf could be considered as a drop-in
substitute for R134a due to similar performance at the same mass flow rate.
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Mendoza-Miranda et al. [83] compared the possibility of replacing R134a with R1234yf,
R1234ze(E) and R450A for variable speed reciprocating compressor. The results of their

CR
analysis indicated that there is a drop in COP of the system for all the three substitutes when
compared with R134a. The COP difference obtained using R1234yf were between 8% and 13%
lower than those obtained with R134a. In the case of R450A, COP differences were ranging
from 4% to 11%. In the case of R1234ze(E), these values were between 4% and 6%. Similar
results were reported by Sieres and Santos [84] considering R1234yf as a drop-in replacement
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for R134a in a small power refrigeration system and Navarro-Esbrí et al. [85] for a vapor
compression system. Theoretical analysis for R1234yf refrigerant use in a hermetic rotary
compressor has also been reported (Jarall [86]). The horizontal convective boiling data for these
refrigerants were reported by Kedzierski and Kang [87].
Navarro et al. [88] tested the possibility of replacing R134a with R1234yf and R290
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refrigerants in an open compressor for bus applications. They reported that while both of the
tested substitutes could be considered as feasible replacement for R134a, yet drop-in
replacement of R1234yf with R134a would result in a 10-15% decrease in the system’s cooling
capacity. Garcia et al. [89] reported the transient response for water refrigeration system of an
evaporator model with R1234yf as a drop-in replacement for R134a. For air-conditioning and
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heat pump applications, an overview for the possibility of replacement of R134a with R1234yf
has been reported by Wang [90].
Mota-Babiloni et al. [91] experimentally compared the performance of vapor
compression system with R1234yf and R1234ze as drop-in replacements for R134a system.
They reported a decrease in the cooling for both substitutes with a significant drop reported for
R1234ze. The COP values were reported 7% lower for R1234yf and 6% lower for R1234ze than
those obtained from R134a. The exergy analysis for these refrigerants has been reported by
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Yataganbaba et al. [92]. Nawaz et al. [93] after several experiments concluded that both
R1234yf & R1234ze(E) refrigerants could be used to replace R134a with comparable
performance without any substantial need for modification in the original system. This was also
reported by Janković et al. [94]. Contrary to that, Sethi et al. [95] reported that minor
modifications are required in these systems. Devecioğlu and Oruç [96] reported that cooling
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capacity and power consumption of R1234ze(E) were lower than R1234yf however the COP of
R1234ze(E) was slightly higher than R1234yf. For application in Organic Rankine Cycle, Molés
et al. [97] reported 13.9% lower net cycle efficiency for R1234yf whereas 13.8% higher net cycle
efficiency for R1234ze substitute for R134a refrigerant. Similar results were also reported by
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Yamada et al. [98] and Invernizzi et al. [99]. Comparison between R1234yf & R1234ze(E) for
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use in ejector based refrigeration reveals that R1234yf could be directly used as a drop-in
replacement however R1234ze(E) needed slight modification (Fang et al. [100]).

CR
The mild flammability of R1234yf and R1234ze(E) decrease the feasibility of this low
GWP refrigerant for domestic uses. To address this issue, Aprea et al. [101, 102, 103]
experimentally tested mixture of R134a/R1234yf & R134a/R1234ze(E) (10/90% by weight) as a
replacement for R134a within domestic refrigerators. This mixture becomes non-flammable with
GWP still less than 150 with satisfactory performance. Lee et al. [104] also reported that above
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10% R134a, the mixture becomes non-flammable. Meng et al. [105] tried the mixture of
R134a/R1234yf (11/89% by mass) for automotive air-conditioning system in place of R134a.
They reported a decrease in the COP of about 4-9% in the cooling mode and 4-16% in the
heating mode.
Sánchez et al. [106] experimentally studied the possibility of drop-in replacement of
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R134a with R290, R600a, R152a, R1234yf & R1234ze(E) low GWP refrigerants. They reported
that R1234yf and R152a could be considered as potential drop-in refrigerants for R134a
whereas R1234ze(E), R600a and R290 are not appropriate for drop-in replacement. Lubricity is
another important property which needs consideration while selecting a replacement refrigerant.
The lubricity of R1234yf is discussed in detail by Akram et al. [107]. Aprea et al. [108] compared
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the refrigerants R134a and R744 in terms of their contribution to global warming for use in
commercial refrigeration system. They concluded that indirect contribution of R744 to global
warming is always higher than that of R134a.
Theoretically Jemaa et al. [109] reported that R1234ze(E) is a suitable alternative for
R134a systems. Experimentally Sánchez et al. [110] showed that R1234ze(E) provides better
results than R152a while considered as a replacement of direct expansion R134a being
converted into indirect system. Mota-Babiloni et al. [111, 112, 113] compared the effectiveness
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of utilizing an internal heat exchanger in a vapor compression system with R1234ze(E) and
R450A as a replacement of R134a. They concluded that the effect of internal heat exchanger is
more significant with R1234ze(E) refrigerant. Aprea et al. [114, 115] reported that R1234ze(E)
could be suitably used a drop-in replacement of R134a for domestic refrigerators. Kabeel et al.
[116] after experiments concluded that R1234ze(E) could be used as a feasible replacement for
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high and medium temperature evaporators however need some suitable modifications when
replacing R134a systems. The heat transfer characteristics of R1234ze(E) as a replacement of
R134a were reported by Longo et al. [117] & Brasz [118] experimentally.
Longo et al. [119] compared the possible utilization of R1234ze(Z) for high temperature
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heat pumps in comparison with R236fa, R134a, R600a & R1234ze(E). They concluded that
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R1234ze(Z) exhibits high heat transfer coefficients and have thermodynamic properties that
makes it comparable to R114 and the most suitable low GWP for application in high

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temperature heat pumps. Similar results have also been reported by Fukuda et al. [120]. The
pVTx properties of R1234ze(E)/R600a mixture has been reported by Cao et al. [121] whereas
the surface tension properties for all HFO were reported by Kondou et al. [122]. Figure 5
summarizes the potential alternatives reported in literature as a replacement for R134A. “Low
COP” corresponds to low COP of alternative compared to R134A as reported in literature
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whereas “High GWP” corresponds to a comparatively higher GWP value when compared with
GWP of all tested alternatives. For R134A, a GWP value higher than 10 for the alternative
refrigerant is considered as “High GWP”. The best candidate alternative refrigerants for R134A
can be shown in Table 5.

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Figure 5 – Summary of the alternatives for R134A as reported in literature.

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Table (5) Thermo-physical properties, safety and environmental data for the best alternative
refrigerants of R134A [148, 149, 150 and 151]

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Boiling Critical Critical
Safety *
Refrigerant Formula Point Temperature Pressure ODP GWP100
Group
(˚C) (˚C) (kPa )
1,1,1,2-Tetrafluoroethane
R134A CH2FCF3
–26 72.707 3761 A1 0.00 4800
1,2-dichloro-1,1,2,2 tetrafluoroethane
R114 CClF2CClF2 3.6 145.7 3260 A1 1.00 10040
1,1-difluoroethane
R152A –24 113.3 4520 A2 0.00 124
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CH3CHF2

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Butane
R600 C4H10
–0.49 151.98 3796 A3 0.00 4
2,3,3,3-tetrafluoro-1 propene
R1234yf CF3CF=CH2
–29.4 94.7 3382.2 A2L 0.00 <1
Trans-1,3,3,3-tetrafluoro-1-propene
R1234ze(E) CF3CH=CHF –18.95 109.37 3636.3 A2L 0.00 <1
Blends (% by mass)
R430A R-152a/600a (76.0/24.0) –26.0 107.16 4089 A3 0.00 110
R-32/152a/1234ze(E)
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R444A (12.0/5.0/83.0) –34.3 102.84 4360.8 A2L 0.00 89

R450A R-134a/1234ze(E) (42.0/58.0) –23.4 104.4 3820 A1 0.00 547

R510A R-E170/600a (88.0/12.0) –25.2 127.8 5331.3 A3 0.00 3
R513A R-1234yf/134a (56.0/44.0) –29.1 96.5 3767 A1 0.00 573
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)
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vii) Alternative Refrigerants for R245fa

R245fa is another refrigerant which has limited use in high temperature heat pumps,
centrifugal chillers, and organic Rankine cycle (ORC) power generation cycles. It is classified as
B1 category refrigerant. It has operating pressures higher than R123 but lower than R134a.
Although this refrigerant does not deplete ozone however it has a GWP of about 858 which
makes it feasible to be replaced. Eyerer et al. [123] concluded after experimental analysis that
R1233zd(E) is a much better drop-in replacement for R245fa while performing at approximately
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6.92% higher thermal efficiency than R245fa in existing organic Rankine power generation
systems. However, Eyerer et al. [124] also reported that R1233zd-E has bad compatibility with
typical polymers compared to R1224yd(Z) and R245fa so more investigation is needed in this
area of interest. Recently Yang et al. [125] reported that there is a 11.4% drop in net power
output of an ORC when using R1233zd-(E) as a drop-in replacement of R245fa however there
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is only 3.1% drop in net power output when using R1234ze(Z). Mateu-Royo et al. [126]
performed a numerical investigation of replacing R245fa with three different olefins in an ORC
equipped with an internal heat exchanger. The results of their analysis indicated that R1233zd-
(E) cause an increase in COP of ORC by 27% compared to R245fa thus performing way better
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than other alternatives. Figure 6 summarizes the potential alternatives reported in literature as a
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replacement for R245fa. “Low COP” corresponds to low COP of alternative compared to R245fa
as reported in literature. Table 6 shows thermo-physical properties, safety and environmental

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data for the alternative refrigerants of R245fa.
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Figure 6 – Summary of the alternatives for R245fa as reported in literature.

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Table (6) Thermo-physical properties, safety and environmental data for the best alternative
refrigerants of R245fa [148, 149, 150 and 151]
Boiling Critical Critical
Safety
Refrigerant Formula Point Temperature Pressure ODP GWP100*
Group
(˚C) (˚C) (kPa )
1,1,1,3,3-pentafluoropropane
R245fa
CF3CH2CHF2
15 154.0 3650 B1 0.00 858
Trans-1-chloro-3,3,3-trifluoro-1-
0.000
R1233zd (E) propene 18 166.6 3620 A1 1
CF3CH=CHCl 24
1-Chloro-2,3,3,3-
0.000
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R1224yd(Z) Tetrafluoropropane 15 156 3340 A1 0.88

CF3-CF=CHCl 23
1,3,3,3-Tetrafluoropropene(z)
R1234ze(Z)
CF3CH=CHF(Z)
9.8 150.1 3530 A2L 0.00 <1
trans-1,1,1,4,4,4-hexafluoro-2-
R1336mzz(E) butene 7.4 137.7 3150 A1 0.00 18
C4H2F6
* Fifth Assessment Report (AR5) Intergovernmental Panel on Climate Change (IPCC)
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viii) Prospects of using Natural Refrigerants as alternative refrigerants

Benhadid-Dib and Benzaoui [127] suggested the use of "natural" refrigerants (such as
CO2 and Ammonia) as a possible solution. Beshr et al. [128] also suggested the use of natural
refrigerant, CO2, and new refrigerant blends as CO2/N40 for supermarket refrigeration systems.
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It was found that low GWP refrigerants decrease the effect of the annual leak rate on the total
system emissions.

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Li Zhanga, et al. [129] reported that R744 and R290 are good future potential
refrigerants. However, the pressure bearing capacity and tightness requirements for equipment
are very high as a low temperature and high pressure refrigerant for R744. Moreover, the
application of R290 refrigerant is restricted because of its inflammable and explosive
characteristics. Also, they suggested that the mixtures of R744 and R290 can be used in auto-
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cascade refrigeration cycle.
Abas et al. [130] reviewed natural and synthetic refrigerants by using Refrigerant
Qualitative Parametric (RQP) quantification model to assist the refrigerant choice decision
process. It was found that CO2 (R744), Ammonia (R717) and Ethane (R170) are good options
among ASHREA envisaged natural refrigerants. However, the flammability and safety are still
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potential challenges in using hydrocarbon refrigerants in heat pump systems.

More recently Ciconkov [131] suggested that R290 has a big potential to be the most
suitable refrigerant for split air conditioning units. The global warming potential becomes the
driving force to use the natural refrigerants in refrigeration cycle (e.g. [132], [133], [134] and
[135]).
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Brodal et al. [136] studied the effect of ambient temperature on the cooling of seawater
using CO2 as a natural refrigerant. They showed that the difference in average COP, with or
without precooling of water in refrigerated tank, is less than 7% for cooling processes from 20°C
to 0°C and also, lower ambient temperature in the Barents Sea results in an average COP of
5.0 compared with 3.0–3.5 in the Mediterranean Sea.
Performance evaluation of a hybrid source heat pump system working with CO2 and
R1234ze (Z) has been presented by Di Wu et al. [137] seeking for improving the system
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performance and energy efficiency. They found that the improvement of COP of the hybrid
source heat pump is 24.8% when R1234ze (Z) condensing temperature is 100°C.
Lychnos et al. [138] designed and built 10 kW cooling capacity hybrid refrigeration
machine working with ammonia mixture R723 (40% Dimethylether, 60% Ammonia) that
combined conventional refrigeration technology with adsorption technology. They concluded
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that the machine can produce maximum 6 kW of cooling power with both systems operating in
parallel (mechanical vapor compression: 4 kW and 2 kW adsorption systems with driving
temperature of 80°C).
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4. Safety impact review

Takizawa et al. [139] experimentally studied the burning velocity, flammability limits, and

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heat of combustion for R1234yf. They found that the burning velocity is slightly increased by
flame stretch at all measured concentrations. Also, the flame propagation of 1234yf is highly
sensitive to the flame temperature and its flammability properties should be considered at
practical temperatures. Ignition hazard evaluation for Propane (R 290), Ethylene (R 1150) and
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A2L refrigerants such as R1234ze, and difluoromethane (R32) has been investigated in [140],

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(2013) [141],[142] and (2015) [143]
Ema et al. [144] presented a review article summarizes data on the reproductive and
developmental toxicity of hydrofluorocarbons (HFCs), including pentafluoroethane (HFC-125),
1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane

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(HFC-152a), difluoromethane (HFC-32) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). They
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found that HFC-32 at approximately 50,000 ppm is maternally and developmentally toxic in rats,
but not in rabbits. HFC-32 has no teratogenicity in rats or rabbits. They stated that there is no
evidence to support the assumption of developmental toxicity in humans and there are no
reports of adverse effect of HFCs in humans. There is limited information about the reproductive
toxicity of HFCs.
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The combustion hazards of refrigerants with low global-warming potential have been
studied in [145] and [146]. Imamura et al. [145] experimentally revealed the data that contribute
to the evaluations of the physical hazard and possibility of the occurrence of a fire. They showed
the profile of the pressure rise and the flame propagation for the burring of R1234ze (E). It was
found that the pressure rise reached a first peak value at about 2.3 kPa, which subsequently
decreased and then the pressure is raised again to reach a second peak value to 4.3 kPa. Also,
they stated that the flame of R1234ze (E) is propagated in a cone shape, therefore the flame
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propagation rate and combustion velocity could not be estimated. And by using the mechanical
ventilation ignition and flame propagation could be prevented.
Davis et al. [146] offered large-scale tests to examine the flammability and explosion
characteristics of low burning velocity substances. R-32, ammonia and 1234yf are considered,
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along with R-152a, methane, propane, and dimethyl ether. They found that mildly flammable
substances have a lower probability of ignition from electrical sources and the influence of
buoyancy on the flame dynamics increased as the burning velocity decreased.
Recently, Feng et al. [147] experimentally investigated the reduction effect of two kinds
of flame retardants on the flammability of R1234yf. The limits of flammability for R1234yf with
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R227ea and R134a and their critical suppression ratios have obtained and analyzed. The flame
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propagation speeds characteristics of R1234yf and its mixtures have been studied. They
concluded that the inhibitory effect of R227ea is better than that of R134a for R1234yf. Also, the

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addition of the flame retardants has a more pronounced effect on the flammability limit of
R1234yf than flame characteristics.
To compare between these candidate alternative refrigerants, a theoretical calculation
has been conducted at −5˚C evaporation temperature and 38˚C condensation temperature to
check the compression ratio of replaced refrigerants with some of their alternatives under the
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same conditions. The results of this comparison are shown in Table 7.

Table (7) Comparison between the compression ratios of replaced refrigerants and their
alternatives

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Compression
Evaporator Condenser
Alternative Replaced Compression ratio of
pressure pressure Application
Refrigerant Refrigerant ratio Replaced
(MPa) (MPa)
Refrigerant
Stationary air
R32 R410A 0.69087 2.35970 3.42 3.49 conditioning systems
Air Conditioning &
R290 R22 0.40619 1.30720 3.22 3.46 Chillers
used as a component
within other refrigerant
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R152A R134A 0.21989 0.86169 3.92 3.96 blends and as a

propellant of aerosol
products
Medium and Low
R448A R404A 0.52500 1.77500 3.38 3.33 Temperatures
Refrigeration
Medium and Low
Temperature
R450A R134A 0.23000 0.85500 3.72 3.96 Refrigeration, Chillers,
Heat Pumps
R513A R507A 0.26937 1.02763 3.81 3.35 Chillers, Heat Pumps
Car air-conditioning
R1234yf R134A 0.26575 0.96769 3.64 3.46
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and Domestic cooling

Chillers and Heat
R1234ze(E) R134A 0.17953 0.72560 4.04 3.46 Pumps
R1233zd(E) R245fa 0.03845 0.20212 5.26 5.43 Low Pressure Chillers

It is seen from table 7 that the candidate alternative refrigerants have compression ratios near
from their baseline refrigerants which indicate a good sound for the compressor in the
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refrigeration cycle. Table 7 shows also the employment of each alternative refrigerant in his
suitable application.
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5. Conclusions & Recommendations

With the increasing level of awareness about the currently in-use high GWP refrigerants,

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significant amount of research have recently been focused on low GWP alternative refrigerants
that could replace the currently used refrigerants. Based on the critical examination of the recent
literature, the following could be concluded about the search of low GWP alternative
refrigerants.

i) R290 has the most potential to be a suitable alternative of R22 and R410A for window
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and split AC systems
ii) R290 has the most potential to be a suitable alternative of R22 for Air Conditioning &
Chillers.
iii) R513A has the most potential to be a suitable alternative of R507A for medium
temperature commercial refrigeration.
iv) L40 & DR7 have the most potential to be a suitable low-flammable replacement for
R404A.
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v) N40 & DR33 have the most potential to be a suitable non-flammable replacement for
R404A.
vi) R1234yf has the most potential to be a suitable low-flammable replacement for R134a
for domestic refrigeration and automotive air-conditioning systems.
vii) R1234yf/R134a has the most potential to be a suitable non-flammable replacement for
R134a for domestic refrigeration and automotive air-conditioning systems.
viii) R1234ze(Z) has the most potential to be a suitable replacement of R134a for high
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temperature heat pump applications.

ix) R1233zd(E) has the most potential to be a suitable replacement of R245fa for existing
organic Rankine systems.

Conclusions from the actual research reveal that search for low GWP alternative
refrigerants is currently a worthy topic of research in the field of refrigeration and air-conditioning
systems. With a lot of research going on in this field, there are still some areas that require
further attention such as,
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ix) Several alternative refrigerants have theoretically being claimed to have potential of
replacing high GWP refrigerants however those claims are yet needed to be verified
experimentally i.e. R429A, R435A, R457A, R430A, etc.
x) It is required to perform the exergy destruction analysis on various components of
refrigerating systems to estimate the effect over the quality of heat transfer process due to
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replacement of high GWP refrigerant with low GWP alternative.

xi) Most of the papers discussed the possibility of replacement of high GWP refrigerants with
low GWP alternatives however only few discusses about the long term compatibility of
those alternatives with the lubricating fluid of the compressor. This is the most critical issue
and needs a thorough review.
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xii) With extreme focus over the technical issues, the economic issue has not been paid much
attention so far as well. While it is important to figure out a suitable low GWP alternative, it
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is also important to assess the economic feasibility of such replacement that involve the
cost of production of those refrigerants in combination with their durability and replacement

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costs.

Acknowledgements

This work has been supported by Saudi Standards, Metrology and Quality Org., Saudi Arabia.
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809, 2017.

[55] L. Creamaschi, X. Wu, A. Biswas, and P. Deokar, “Experimental study of compressor operating
characteristics and performance when using refrigerants R32, R1234yf, and two new low GWP
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their Syst., pp. 57–76, 2013.

[56] G. A. Longo, S. Mancin, G. Righetti, and C. Zilio, “HFC32, a low GWP substitute for HFC410A
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in medium size chillers and heat pumps,” Int. J. Refrig., vol. 53, pp. 62–68, 2015.

[57] F. Botticella, F. de Rossi, A. W. Mauro, G. P. Vanoli, and L. Viscito, “Multi-criteria

(thermodynamic, economic and environmental) analysis of possible design options for
residential heating split systems working with low GWP refrigerants,” Int. J. Refrig., 2018.

[58] S. In, K. Cho, B. Lim, and C. Lee, “Partial load performance test of residential heat pump
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system with low-GWP refrigerants,” Appl. Therm. Eng., vol. 85, pp. 179–187, 2015.
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[59] S. In, K. Cho, B. Lim, H. Kim, and B. Youn, “Performance test of residential heat pump after
partial optimization using low GWP refrigerants,” Appl. Therm. Eng., vol. 72, no. 2, pp. 315–
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[61] A. Alabdulkarem, R. Eldeeb, Y. Hwang, V. Aute, and R. Radermacher, “Testing, simulation and
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[62] A. Mota-Babiloni, P. Makhnatch, and R. Khodabandeh, “Recent investigations in HFCs
substitution with lower GWP synthetic alternatives: Focus on energetic performance and
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[63] P. Makhnatch, A. Mota-Babiloni, and R. Khodabandeh, “Experimental study of R450A drop-in

performance in an R134a small capacity refrigeration unit,” Int. J. Refrig., vol. 84, pp. 26–35,
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[64] S. J. Lee, B. H. Shon, C. W. Jung, and Y. T. Kang, “A novel type solar assisted heat pump
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to R134a in domestic refrigerators,” Energy Sustain. Dev., vol. 17, no. 5, pp. 471–476, 2013.
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[66] A. Mota-Babiloni, P. Makhnatch, R. Khodabandeh, and J. Navarro-Esbrí, “Experimental

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[67] M. Rasti, S. Aghamiri, and M. S. Hatamipour, “Energy efficiency enhancement of a domestic

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[68] R. Cabello, D. Sánchez, R. Llopis, I. Arauzo, and E. Torrella, “Experimental comparison

between R152a and R134a working in a refrigeration facility equipped with a hermetic
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study of an R1234ze(E)/R134a mixture (R450A) as R134a replacement,” Int. J. Refrig., vol. 51,
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[71] G. Li, M. Eisele, H. Lee, Y. Hwang, and R. Radermacher, “Experimental investigation of energy
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R134a and Its Alternative Refrigerants,” Energy Procedia, vol. 109, no. November 2016, pp.
153–160, 2017.
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[73] A. G. Devecioğlu and V. Oruç, “An analysis on the comparison of low-GWP refrigerants to
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[74] S. Daviran, A. Kasaeian, S. Golzari, O. Mahian, S. Nasirivatan, and S. Wongwises, “A
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[75] S. Golzari, A. Kasaeian, S. Daviran, O. Mahian, S. Wongwises, and A. Z. Sahin, “Second law
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automotive air conditioning systems using refrigerant R1234yf at various compressor speeds,”
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[77] F. Molés, J. Navarro-Esbrí, B. Peris, A. Mota-Babiloni, and Á. Barragán-Cervera, “Theoretical

energy performance evaluation of different single stage vapour compression refrigeration
configurations using R1234yf and R1234ze(E) as working fluids,” Int. J. Refrig., vol. 44, pp.
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[79] S. Bobbo, C. Zilio, M. Scattolini, and L. Fedele, “R1234yf as a substitute of R134a in

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[80] C. Aprea, A. Greco, and A. Maiorino, “An experimental investigation on the substitution of
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[82] G. Righetti, C. Zilio, and G. A. Longo, “Comparative performance analysis of the low GWP
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[85] J. Navarro-Esbrí, J. M. Mendoza-Miranda, A. Mota-Babiloni, A. Barragán-Cervera, and J. M.

Belman-Flores, “Experimental analysis of R1234yf as a drop-in replacement for R134a in a
vapor compression system,” Int. J. Refrig., vol. 36, no. 3, pp. 870–880, 2013.

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within a micro-fin tube,” Int. J. Refrig., vol. 88, pp. 538–551, 2018.
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[100] Y. Fang, S. Croquer, S. Poncet, Z. Aidoun, and Y. Bartosiewicz, “Drop-in replacement in a

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[101] C. Aprea, A. Greco, and A. Maiorino, “An experimental investigation of the energetic
performances of HFO1234yf and its binary mixtures with HFC134a in a household refrigerator,”
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[102] C. Aprea, A. Greco, and A. Maiorino, “Comparative performance analysis of

HFO1234ze/HFC134a binary mixtures working as a drop-in of HFC134a in a domestic
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[103] C. Aprea1, A. Greco, and A. Maiorino, “HFOs and their binary mixtures with HFC134a working
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[106] D. Sánchez, R. Cabello, R. Llopis, I. Arauzo, J. Catalán-Gil, and E. Torrella, “Energy

performance evaluation of R1234yf, R1234ze(E), R600a, R290 and R152a as low-GWP R134a
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analysis of an internal heat exchanger in a vapour compression system using R1234ze(E) and
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[115] C. Aprea, A. Greco, A. Maiorino, and C. Masselli, “The drop-in of HFC134a with HFO1234ze in
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