Journal of Power Technologies 100 (3) (2020) 232–239

Critical evaluation of R134a, R1234yf and R744 in passenger car

cooling systems
Jan Grygierzec ∗, Sebastian Werle †

Abstract has become a key trend in the AS, driven by clean

The Montreal Protocol on ozone-depleting substances and the
energy and climate-change concerns such as support
Kyoto Protocol to the United Nations Framework Convention zero-emission vehicles and carbon taxes – intended to
on Climate Change are affecting the refrigeration industry. Both reduce greenhouse gasses emissions. One important
documents have banned the use of substances responsible for element of this transformation is air conditioning (AC)
ozone depletion and global warming. The automotive indus-
try must keep up with these changes. The design of cooling systems in electric cars (ECs).
systems in cars must meet the requirements of new refrigerants.
On September 16, 1987, in Montreal, over 160 coun-
In addition, changing the production profile of large car compa- tries signed a protocol to counteract the degeneration
nies towards electric and hybrid cars increases this need. This of the ozone layer. The key point of the document
development has a significant impact on the solutions installed was to reduce or totally eliminate refrigerants, which
in passenger vehicles. The paper presents a critical assessment significantly affect the destruction of the ozone layer
of R134a, R1234yf, and R744 in passenger car heat pump sys- and increase global warming.
tems. The possibility of their use in common air conditioning
systems with motor drive and in the heat pump of an electric International agreements have significantly affected
vehicle was presented. The calculation algorithm of the heat the automotive industry. The refrigerants used have
pump system has been developed, showing the influence of the been subject to restrictions and actions have been ini-
tiated to obtain solutions compliant with the regu-
physical properties of refrigerants on efficiency during the pro-
cess of the designed heat pump system. The impact of using lations. The EU has also introduced F-Gas regula-
new refrigerants in the car production process has been ana- tion [3], monitoring and limiting the automotive use
lyzed and commented on. The influence of thermodynamic and of refrigerants.
ecological properties of refrigerants on the process of designing
The car industry over the years has moved away from
a heat pump system using a calculation model was described.
AC systems using chlorofluorocarbons (CFCs) and hy-
Types of heat pump in electric cars and a calculation model
drochlorofluorocarbons (HFCFs) and has started in-
were presented.
troducing hydrofluorocarbons (HFCs). AC systems
have been adapted to 1,1,1,2-tetrafluoroethane R-
Keywords: R134a, R1234yf, R744, Heat pump, Car, 134a after dichlorodifluoromethane R-12. In accor-
Air-conditioning dance with the current legal regulations related to the
influence of AC refrigerants on the environment the
R-134a refrigerant from the CFC group was replaced
1 Introduction by the R-134a refrigerant belonging to the HFC group.
Subsequent legal regulations, caused by the negative
influence of refrigerants on global warming, imposed
The automotive sector (AS) is an important sector
restrictions on the use of R-134a in AC devices in mo-
for the European Union (EU) economy, employing
tor vehicles, mainly due to the high value of the GWP
more than 8 million people. The electric vehicle is an
(Global Warming Potential) index.
increasingly important component of the global car
fleet [1] The global stock of electric passenger cars As a consequence of these restrictions, natural refrig-
reached 3.1 million in 2017, an increase of 57% on erants seem to be the best solution in the refrigeration
the previous year, and BEVs account for two-thirds industry [4]. The changes and regulations affecting
of the world’s electric car fleet according to an IEA AC systems are driving the development of systems
report of 2018 [2]. The automotive sector is currently with refrigerants that have a negligible impact on the
in the middle of a transformation, caused mainly by environment. One alternative to R-134a is R-1234yf
environmental issues. The electrification of vehicles belonging to the HFO (hydrofluoroolefin) group. This
∗ Silesian University of Technology, e-mail refrigerant is the subject of numerous studies. Accord-
† Silesian University of Technology, e-mail ing to Gaurav and Raj Kumar [5] the refrigerant mix-
Journal of Power Technologies 100 (3) (2020) 232–239

ture R-134a/R-1234yf/R-1234ze (40%/22%/38%) is

Table 1: Properties of refrigerants
only one replacement option for R-134a. This result
shows that the interchangeability of R-134a with R- R134a R1234yf R744 Unit
1234yf mixture is possible without any changes in the Formula CH2FCF3CF3CF CO2
design of the system. R-1234yf is characterized by a =
low GWP of 4. This value is 350 times lower than for CH2
R-134a. An additional feature of R-1234yf is that the Chemical 811- 754- 124-
decomposition time of R-1234yf is 11 days. This is Abstracts 97-2 12-1 38-9
a huge advantage over R-134a, whose decomposition Service
number
time is 13 years [6] Due to this difference AC sys-
Molecular 102 114 44 g·mol
tems designed for R-134a must be redesigned before
mass -1
the new refrigerant can be used. ODP 0 0 0
Another refrigerant commonly used is carbon dioxide. GWP100 1300a <1a 1
Carbon dioxide was one of the first refrigerants used Safety A1 A2L A1
classification
in AC. Alexander Twining proposed the use of it in a
Critical 374.21 367.85 304.1 K
British patent in 1850 [7]. Due to the appearance of temperature
AC refrigerants from CFC and HCFC groups carbon c
dioxide was used less frequently. Due to their speci- Critical 4.06 3.38 7.37 MPa
ficity and thermodynamic properties, carbon dioxide pressure c
was replaced with substances from the CFC and HCFC Density of 1206 1091.91 1101 kg
groups. liquid (at (at (at - m-
25oCd) 0oCd) 37oCd) 3
In ECs the AC system, which is the most energy de- Density of 8.288 37.92 1.997 kg
manding auxiliary component, plays a significant role saturated (at (at (at m-
in providing comfort during driving and energy uti- stem 15oCd) 25oCd) 0oCd) 3
lization. The paper presents a critical evaluation of
R134a, R1234yf. and R744 in cooling systems of pas-
senger cars. The possibility of using them in common
AC systems in a car with the motor drive and in the properties. It has a higher density than atmospheric
heat pump of the electric vehicle is presented. The oxygen, which means it has the possibility of displac-
influence of use of the new refrigerant in the vehicle ing it in closed areas. It is perceptible in the air by its
industry was analyzed and commented. The thermo- ether smell and inhalation may result in nausea and
dynamics and ecological aspects were analyzed. dizziness. The factor was used by most companies
producing vehicles and competition between manufac-
turers led to widespread use of the systems in light of
2 Description of the refrigerants their efficiency and weight. The service infrastructure
during this period has gained knowledge and experi-
Table 1 shows the functional parameters of refriger- ence regarding the systems, which reduces the time of
ants. diagnostics and service. New designs of AC systems
for R134a factor in vehicles until 2017 reduced all sys-
a
IPCC (The Intergovernmental Panel on Climate tem defects previously encountered. Through compe-
Change) 5th report, chapter 8 [8] tition, the systems have been improved and developed
b
ANSI/ASHRAE standard 34-2013 (A-non-toxic, over the years. Many companies supplying elements
1- non-flammable, 2L- mildly flammable 3 – for AC systems have developed production methods
flammable) [9] which reduce the failure of the system. The refriger-
ant self-ignites at 405°C, resulting in harmful hydro-
c
REFPROP (REFerence fluid PROPerties) 9.1 [10] gen fluoride. It has an ether fragrance and a low GWP
d index. Typical methods for producing HFO-1234yf
Calm and Hourahan 2011[11]
start with 1,2,3,3,3-pentafluoropropene. Hydrogenati-
R134a was introduced as a substitute for R12 due to on of this alkene gives 1,2,3,3,3-pentafluoropropane,
its lower ecological harmfulness. Because of the re- which upon heating with an Al-based catalyst under-
strictions related to refrigeration systems in 2017, the goes dehydrofluorination [8] In the early 20th century,
use of R12 was banned in new AC car systems. This carbon dioxide was a popular solution in AC systems.
restriction precludes the use of R134a in future AC After 1940 it was supplanted by synthetic substan-
systems in electric cars too. The gas is stable un- ces. The solution with dry ice was used in other ty-
der normal conditions and does not have flammable pes of devices that keep the temperature low. Due to

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Journal of Power Technologies 100 (3) (2020) 232–239

the low temperature of the critical point, circulation 4 Environmental impact

of the refrigerant is supercritical. The first commer-
cial devices with an overcurrent circuit appeared on
the market only in 1999, and commercial refrigerati- Policy targeting the negative impact of refrigerants on
on appliances only in 2003 [12] Carbon dioxide has a the environment also sets time periods for the with-
very low critical temperature, which distinguishes it drawal of some of these substances. This derives di-
from the other factors. R744 is characterized by high rectly from EU law and forms part of a sustainable
pressure in the installation from 30 to 130 bar. Such development policy [18]. In accordance with Regu-
high-pressure forces duly selected wires and increase lation (EC) No. 1005/2009 of the European Parlia-
the sensitivity of the system to unsealing. R744 uses ment and of the Council of 16th of September 2009
gas coolers that can be used in a heat pump, it is a on substances that deplete ozone, production of coar-
good alternative to electric vehicles in which the tem- se HCFC agents will cease in 2020. The limitations
perature of the battery is often under the control of on refrigerants are related to indicators determining
the AC system. The system forces the gas radiator to the impact on the natural environment. ODP Ozone
be used in a heat pump; carbon dioxide is an odorless Depletion Potential for R-11 factor for which ODP
gas that does not show flammable properties. R744 is is 1. Refrigerants and their impact on the environ-
a natural refrigerant with a low potential of creating ment are determined in accordance with the ODP
a greenhouse effect. Carbon dioxide can be obtained and GWP indicators. According to the values in Fi-
by distillation from air, but the method is inefficient. gure 1, the values for all discussed factors are at level
Industrially, carbon dioxide is predominantly an unre- 0. Global Warming Potential is the main determinant
covered waste product, produced by several methods of changes introduced on the market of refrigerants;
which may be practiced at various scales [13]. R1234yf and R744 have a similar value and current-
ly both meet requirements. As reported [19], it ap-
pears that the intermediates used in the preparation
of R1234yf are substances from the HCFC group of
3 Comparison of operating para- hydrofluorocarbons, which are controlled substances
that have a negative effect on the ozone layer. Sub-
meters of refrigerants stances from the HCFC group are subject to restricti-
ons. Also affecting the legitimacy of choice of the AC
Reasor et al. (Reasor et al. 2010) [14] carried out refrigerant are substances formed during the decom-
thermodynamic simulations using various types of ref- position reaction. R1234yf after entering the atmos-
rigerants. The studies carried out included R134a and phere forms trifluoroacetic acid, which is an organic
R1234yf. Indicating that R1234yf has a 40% higher carboxylic acid about 10,000 times more potent than
pressure drop in the exchanger than R134a, the au- acetic acid. The ISO817 standard indicates two clas-
thors conclude that R-1234yf may not be as good a ses of toxicity of refrigerants: low-toxicity and high
replacement for R-134a as is generally assumed. In toxicity. The classes are expressed in the occupational
2013 Kwang-Li [15] performed tests to determine and Exposure Limit OEL indicator. The amount of refri-
compare the heat transfer coefficient in the evapo- gerant during work related to refrigerant systems is
ration process for natural refrigerants and R-1234yf. determined according to the parameter. According to
This experiment showed that of all refrigerants CO2 the information in Tab.??, it is indicated that the OEL
showed the best heat transfer coefficient. Brown et for compressed refrigerants meets the conditions for
al. [16] performed simulations in 2002 that compare low-toxic gases below 400 ppm. At the same time,
R134a and R744. They showed that R744 has wor- due to the harmful acid appearing in certain condi-
se operating parameters in similar conditions. Mota- tions with R1234yf, SAE international in 2007-2009,
Babiloni et al. [17] in 2015 conducted an experiment together with Audi, BMW, Chrysler, Daimler, Ford,
comparing R1234yf and R134a. The test result sho- GM, Renault, Jaguar Land Rover, and Toyota carried
wed that the internal exchanger clearly improves the out research on the combustibility of the refrigerant
efficiency of the system with R1234yf. This is proof during operation and accidents. No ignition was found
of the unquestionably better performance of R134a in under the test conditions or during an accident at a
a traditional AC system without an internal heat ex- speed of 70 km / h. The average ignition tempera-
changer. At the same time, the values of GWP for the ture for R1234yf is 405o C. Is not possible to exclude
synthetics clearly indicate that natural R744 can be a the occurrence of the said temperature during an ac-
substitute that meets all restrictions regarding the use cident. R744 is a natural factor that is nontoxic and
of refrigerants. The comparison was made to illustrate its increased level in the air is manifested by the di-
the environmental impact of the refrigerants and the sturbance of vital functions. At the same time, the
differences in performance used in system design. level of carbon dioxide already in low concentrations

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Journal of Power Technologies 100 (3) (2020) 232–239

in high-value vehicles, but this is the first step to im-

Table 2: Environmental properties
plementing this technology in other models. Future
Refrigerant R134a R1234yf R744 solutions for combustion engine vehicles or electric ve-
hicles with one type of refrigerant would reduce the
Combustibility 1 2L 1 cost of validation.
Ignition temp - 405oC -
Flammability YES 6.2- YES
limit 12.3%
Safety class A1 A2L A1
6 Heat pump systems
ODP/GWP 0/1400 0/4 0/1
Currently, various types of heat pump systems are
used. The heat pump used in the Nissan Leaf (Fig.
affects the level of comfort and concentration, which 1.) is a set of three heat exchangers, two expansion
is why CO2 level sensors installed in cars to moni- valves (I, III), a three-way valve (II), a bypass valve
tor air quality can also perform an additional warning (II), an airflow blocker and an electric AC compressor.
function after the possible unsealing of an AC system During operation on hot days, the internal condenser
using R744 refrigerant. is bypassed, the heating circuit expansion valve (IV)
is bypassed by opening the bypass valve, and the ex-
ternal heat exchanger works in condenser mode.

5 Industry potential
Air conditioning systems in vehicles can be divided
into three categories:
-currently used - available in new vehicles -future so-
lutions
Currently used vehicles have installations for refriger-
ant R134a and R1234yf and theoretically R744 (Daim-
ler offers a new model with R744). Adapting old AC Figure 1: Nissan Leaf heating-cooling system diagram
systems to different refrigerants requires modifications ( I III expansion valve, II three-way valve , IV bypass
in the basic system by specialists. The automotive )
industry does not provide that kind of modification,
meaning that the AC system is designed for one kind
During cold days, the airflow through the internal con-
of refrigerant. Companies producing elements of AC
denser heats the passenger compartment. The expan-
systems have guidelines from the manufacturer re-
sion valve (I) and internal evaporator are omitted by
garding not only the parameters of the system but
setting the three-way valve (II). The bypass valve is
also specific requirements for working conditions pro-
closed in parallel, which causes the refrigerant to flow
vided for only one refrigerant. Requirements for AC
through the expansion valve. When the humidity level
pipe systems are for example related to resistance to
is increased, it is possible to run the evaporator and
working pressure and the effect of vibrations from the
the internal condenser at the same time using a three-
internal combustion engine. In electric vehicles re-
way valve and a bypass valve.
quirements for an AC loop are created to resist the
lowest level of vibration but also have higher noise The solutions used differ from one company to an-
requirements. That creates differences in every type other, the American company Tesla uses a different
of refrigerant and also the type of vehicle. Currently, type of system in its electric vehicles. During cold
the design of AC systems is carried out simultaneously days, heat is taken from the fluid cycle of electric mo-
with the design of other systems in vehicles. This so- tors and electronics. This heat can be supplied to the
lution allows effective use of the working space in ve- cabin circulation, bypassing the liquid at higher tem-
hicles, also limiting the possibility of future changes. peratures to the circulation using a three-way valve
From the economical point of view a future solution (II). This allows you to control the temperature of
with one type of refrigerant is the best way to lower the engines and electronics in the electric car. On hot
the cost of validation. The fact that AC systems with days, the refrigeration circuit increases its efficiency
R744 are now available in new vehicles means the and exchanges heat with the cabin circuit in the heat
technology has completed the validation process and exchanger. Mitsubishi Motors Corporation has intro-
is safe for use. The new AC systems are offered only duced a system consisting of a refrigeration cycle, en-

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Journal of Power Technologies 100 (3) (2020) 232–239

Figure 2: Tesla Model S heating-cooling system dia-

gram (I II three-way valve)

gine cycle, and passenger compartment circuit. Dur-

ing hot days, the heat in the cabin is dissipated in the
evaporator. On cold days, an electric heater in the
cabin circuit is used.

Figure 3: Mitsubishi i-MIEV (I three-way valve)

7 Heat pump calculation

methodology
The calculation conditions used when designing the
heat pump are in each case matched to the refriger-
ant, the type of vehicle and the conditions in which
it will be operated The methodologies presented be-
low should be interpreted individually by selecting the
appropriate parameters. This model was presented
for a theoretical circuit consisting of a compressor,
evaporator, expansion valve, and condenser. Properly
adopted points correspond to:
I. The evaporated refrigerant in the gas phase in front
of the compressor
II. The compressed refrigerant in the gas phase with
increased pressure at the exit from the compressor
III. The condensed refrigerant in the liquid phase at
the outlet of the condenser
IV. Refrigerant before the evaporator

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Journal of Power Technologies 100 (3) (2020) 232–239

hI = f (XI TI ) Q̇compr = ṁcz × (hII − hI )

where: hI - enthalpy in point I[kJ/kg], XI - degree of where: Qcompr - - heat flux of the air stream sup-
dryness of the factor in point I [-], TI -temperature at a plied to the evaporator [kW]. The vehicle’s low ambi-
point I [o C]. The equation shows that Enthalpy at the ent temperature heating mode is supported by electric
point I. The enthalpy in point II and II is calculated heaters that increase the air temperature, minimizing
in the same way as in point I the airflow. When the ambient temperature at a point
I is higher, the air supply to the evaporator is blocked
hIIs − hI and the refrigerant is heated by an electric heater.
hII = hI +
ηIs The heat of the air stream is supplied to the evapo-
rator [kW].
where: hII - enthalpy in point II[kJ/kg], hIIs - enthalpy
in point II for isentropic compression [kJ/kg], his com-
pressor internal efficiency [-]. Q̇heater = ṁa,evap × cp,a (Tmin − Tot )

where: Qheater - heat flux of the air stream sup-

hIV = f (PI hIII )
plied to the evaporator [kW], Tmin - minimum required
air temperature to the evaporator[o C] Formula for the
where: hIV - enthalpy in point IV[kJ/kg], hIII - en-
COP factor during heating mode:
thalpy in point III[kJ/kg], PI -pressure at point I
[MPa]. In the next stage, the formulas for calculating
the heat stream transferred in each heat exchanger Q̇a,cond + Q̇heater
COPheat =
are presented. Q̇compr

Q̇cz = ṁcz × (hII − hIII ) The formula for the COP factor during cooling mode:

where: Qcz - heat flow transferred in the con- Q̇a,evap

denser [kW], cz - mass stream of circulating refriger- COPcooling =
ant[kg/s]. Q̇compr

The computational methodology is based on input

Q̇p = ṁcz × (hI − hIV ) data. The parameters of refrigerants such as R134a,
R1234yf, and R744 are based on reliable materials.
where: Qp - heat flow transferred in the evaporator Accordingly, the multitude of situations related to
[kW]. The formulae for the evaporator and condenser temperature, humidity and the speed of movement in-
air streams determined from their mass streams are creases the number of conditions that should be simu-
presented below. lated. The algorithm represents the design aspects to
be taken into account when selecting the appropriate
refrigerant to be used in AC systems due to the system
Q̇s = Q̇a,cond = ṁa,cond × cp,a (Taim − Tot ) efficiency factor. Differences in the functional param-
eters of the individual factors significantly affect the
COP of the designed system. Electric cars already
where: Qa, cond - heat flux of the air stream supplied
meet the environmental requirements, which augurs
to the condenser [kW], a, cond - mass stream supplied
well for their future share in the automotive market.
to the condenser [kg/s].cp, a - specific heat of air [
The heat pump system clearly meets the requirements
kJ/kgK ], Taim - the desired temperature of air sup-
for maintaining air parameters in the passenger com-
plied to the cabin [o C]. TI - ambient temperature [o C].
partment. All additional heat pump functions will af-
The following parameters are required to calculate the
fect overall performance accountability. A heat pump
evaporator energy and compressor power.
with an additional system to control the temperature
conditions of the battery will have valves and a pump,
Q̇p = Q̇a,evap = ṁa,evap × cp,a (Tot − TI ) increasing the weight of the vehicle and using energy.
A multitude of solutions will also be associated with
where: Q a,evap - heat of the air stream supplied to an increase in the number of valves and lines filled
the evaporator [kW], a,evap - mass stream supplied with medium. All these elements will add to elements
to the evaporator [kg/s]. that negatively affect the range of the vehicle.

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Journal of Power Technologies 100 (3) (2020) 232–239

8 Conclusions Physical, Safety, and Environmental Data for Current

and Alternative Refrigerants.
Vehicles, regardless of the manufacturer, have solu- 7. (2010) 9th IIR Gustav Lorentzen Conference 2010
tions that fall into the group of heat pumps. What- - natural refrigerants – real alternatives, Sydney, April
ever the type of system, the principle of operation 12-14,. CO2 - A refrigerant from the past with
is similar. Due to current regulations, the refrigerant prospects of being one of the main refrigerants in the
that is widely used at present is R1234yf. A car’s heat future.
pump performs many tasks and its operation signifi-
cantly affects the range of the vehicle. Current sys- 8. (2008) Process to manufacture 2,3,3,3-
tems have an increased level of complexity compared tetrafluoropropene. PCT Int. Appl., WO
to systems used only for cooling. The presented cal- 2008030440 A2 20080313.
culation method has many stages. At the calcula-
9.Myhre, G., Shindell, D., Bréon, F.-M., Collins, W.,
tion stage, real input data must be available. Due
Fuglestvedt, J., Huang, J., Koch, D., Lamarque, J.-
to the mechanical complexity of the systems and var-
F., Lee, D., Mendoza, B., Nakajima, T., Robock, A.,
ious climatic conditions, it is difficult to enter input
Stephens, G., Takemura, T., and Zhang, H. (2013)
data correctly into the calculations. In light of the
Anthropogenic and natural radiative forcing, in Cli-
solutions used at present, it is advisable to validate
mate Change 2013: The Physical Science Basis. Con-
calculations in real conditions under different climatic
tribution of Working Group I to the Fifth Assessment
conditions for the current refrigerant. The validation
Report of the Intergovernmental Panel on Climate
process should be based on the validation of the cal-
Change (eds.Stocker, T.F., Qin, D., Plattner, G.-K.,
culation assumptions made during the design process
Tignor, M., Allen, S.K., Doschung, J., Nauels, A.,
and should take into account the impact of the com-
Xia, Y., Bex, V., and Midgley, P.M.), Cambridge Uni-
plexity of the system in the overall energy accounting
versity Press, Cambridge, UK, pp. 659–740.
of the system to create appropriate combinations of
input parameters for heat pumps designed to work on 10.Standard, A.S.H.R.A.E. (2008) Designation and
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11.Lemmon, E.W., Huber, M.L., and McLinden,
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