Lesson

26
Refrigerants
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The specific objectives of this lecture are to:
1. Discuss the importance of selection of suitable refrigerant in a refrigeration
system (Section 26.1)
2. Classify refrigerants into primary and secondary, and discuss the important
differences between primary and secondary refrigerants (Section 26.2)
3. Discuss refrigerant selection criteria based on thermodynamic, thermophysical,
environmental and economic properties (Section 26.3)
4. Describe the numbering system used for designating refrigerants (Section
26.4)
5. Present a comparison between different refrigerants (Section 26.5)

At the end of the lecture, the student should be able to:

1. Explain the importance of refrigerant selection

2. Differentiate between primary and secondary refrigerants
3. List the criteria used in selecting refrigerants
4. List important thermodynamic and environmental properties influencing
refrigerant selection
5. Write the chemical formula of a refrigerant from its number
6. Compare different refrigerants and suggest replacements for CFCs and
HCFCs

26.1. Introduction:
The thermodynamic efficiency of a refrigeration system depends mainly on
its operating temperatures. However, important practical issues such as the
system design, size, initial and operating costs, safety, reliability, and
serviceability etc. depend very much on the type of refrigerant selected for a
given application. Due to several environmental issues such as ozone layer
depletion and global warming and their relation to the various refrigerants used,
the selection of suitable refrigerant has become one of the most important issues
in recent times. Replacement of an existing refrigerant by a completely new
refrigerant, for whatever reason, is an expensive proposition as it may call for
several changes in the design and manufacturing of refrigeration systems. Hence
it is very important to understand the issues related to the selection and use of
refrigerants. In principle, any fluid can be used as a refrigerant. Air used in an air
cycle refrigeration system can also be considered as a refrigerant. However, in
this lecture the attention is mainly focused on those fluids that can be used as
refrigerants in vapour compression refrigeration systems only.

26.2. Primary and secondary refrigerants:

Fluids suitable for refrigeration purposes can be classified into primary and
secondary refrigerants. Primary refrigerants are those fluids, which are used
directly as working fluids, for example in vapour compression and vapour
absorption refrigeration systems. When used in compression or absorption
systems, these fluids provide refrigeration by undergoing a phase change
process in the evaporator. As the name implies, secondary refrigerants are those
liquids, which are used for transporting thermal energy from one location to other.
Secondary refrigerants are also known under the name brines or antifreezes. Of

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course, if the operating temperatures are above 0oC, then pure water can also be
used as secondary refrigerant, for example in large air conditioning systems.
Antifreezes or brines are used when refrigeration is required at sub-zero
temperatures. Unlike primary refrigerants, the secondary refrigerants do not
undergo phase change as they transport energy from one location to other. An
important property of a secondary refrigerant is its freezing point. Generally, the
freezing point of a brine will be lower than the freezing point of its constituents.
The temperature at which freezing of a brine takes place its depends on its
concentration. The concentration at which a lowest temperature can be reached
without solidification is called as eutectic point. The commonly used secondary
refrigerants are the solutions of water and ethylene glycol, propylene glycol or
calcium chloride. These solutions are known under the general name of brines.

In this lecture attention is focused on primary refrigerants used mainly in

vapour compression refrigeration systems. As discussed earlier, in an absorption
refrigeration system, a refrigerant and absorbent combination is used as the
working fluid.

26.3. Refrigerant selection criteria:

Selection of refrigerant for a particular application is based on the following
requirements:

i. Thermodynamic and thermo-physical properties

ii. Environmental and safety properties, and
iii. Economics

26.3.1. Thermodynamic and thermo-physical properties:

The requirements are:

a) Suction pressure: At a given evaporator temperature, the saturation pressure

should be above atmospheric for prevention of air or moisture ingress into the
system and ease of leak detection. Higher suction pressure is better as it leads to
smaller compressor displacement

b) Discharge pressure: At a given condenser temperature, the discharge

pressure should be as small as possible to allow light-weight construction of
compressor, condenser etc.

c) Pressure ratio: Should be as small as possible for high volumetric efficiency

and low power consumption

d) Latent heat of vaporization: Should be as large as possible so that the required

mass flow rate per unit cooling capacity will be small

The above requirements are somewhat contradictory, as the operating

pressures, temperatures and latent heat of vaporization are related by Clausius-
Clapeyron Equation:

h fg s fg
ln (Psat ) = − + (26.1)
RT R

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In the above equation, Psat is the saturation pressure (in atm.) at a temperature
T(in Kelvin), hfg and sfg are enthalpy and entropy of vaporization and R is the gas
constant. Since the change in entropy of vaporization is relatively small, from the
above equation it can be shown that:

Pc ⎡ h fg ⎛ 1 1 ⎞⎤
= exp ⎢ ⎜⎜ − ⎟⎟ ⎥ (26.2)
Pe ⎢⎣ R ⎝ Te Tc ⎠ ⎥⎦

In the above equation, Pc and Pe are the condenser and evaporator

pressures, Tc and Te are condenser and evaporator temperatures. From the
above equation, it can be seen that for given condenser and evaporator
temperatures as the latent heat of vaporization increases, the pressure ratio also
increases. Hence a trade-off is required between the latent heat of vaporization
and pressure ratio.

In addition to the above properties; the following properties are also

important:

e) Isentropic index of compression: Should be as small as possible so that the

temperature rise during compression will be small

f) Liquid specific heat: Should be small so that degree of subcooling will be large
leading to smaller amount of flash gas at evaporator inlet

g) Vapour specific heat: Should be large so that the degree of superheating will
be small

h) Thermal conductivity: Thermal conductivity in both liquid as well as vapour

phase should be high for higher heat transfer coefficients

i) Viscosity: Viscosity should be small in both liquid and vapour phases for
smaller frictional pressure drops

The thermodynamic properties are interrelated and mainly depend on

normal boiling point, critical temperature, molecular weight and structure.

The normal boiling point indicates the useful temperature levels as it is

directly related to the operating pressures. A high critical temperature yields
higher COP due to smaller compressor superheat and smaller flash gas losses.
On the other hand since the vapour pressure will be low when critical
temperature is high, the volumetric capacity will be lower for refrigerants with high
critical temperatures. This once again shows a need for trade-off between high
COP and high volumetric capacity. It is observed that for most of the refrigerants
the ratio of normal boiling point to critical temperature is in the range of 0.6 to 0.7.
Thus the normal boiling point is a good indicator of the critical temperature of the
refrigerant.

The important properties such as latent heat of vaporization and specific

heat depend on the molecular weight and structure of the molecule. Trouton’s
rule shows that the latent heat of vaporization will be high for refrigerants having
lower molecular weight. The specific heat of refrigerant is related to the structure
of the molecule. If specific heat of refrigerant vapour is low then the shape of the
vapour dome will be such that the compression process starting with a saturated
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point terminates in the superheated zone (i.e, compression process will be
dry). However, a small value of vapour specific heat indicates higher degree of
superheat. Since vapour and liquid specific heats are also related, a large value
of vapour specific heat results in a higher value of liquid specific heat, leading to
higher flash gas losses. Studies show that in general the optimum value of molar
vapour specific heat lies in the range of 40 to 100 kJ/kmol.K.

The freezing point of the refrigerant should be lower than the lowest
operating temperature of the cycle to prevent blockage of refrigerant pipelines.

26.3.2. Environmental and safety properties:

Next to thermodynamic and thermophysical properties, the environmental

and safety properties are very important. In fact, at present the environment
friendliness of the refrigerant is a major factor in deciding the usefulness of a
particular refrigerant. The important environmental and safety properties are:

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

b) Global Warming Potential (GWP): Refrigerants should have as low a GWP

value as possible to minimize the problem of global warming. Refrigerants with
zero ODP but a high value of GWP (e.g. R134a) are likely to be regulated in
future.

c) Total Equivalent Warming Index (TEWI): The factor TEWI considers both
direct (due to release into atmosphere) and indirect (through energy
consumption) contributions of refrigerants to global warming. Naturally,
refrigerants with as a low a value of TEWI are preferable from global warming
point of view.

d) Toxicity: Ideally, refrigerants used in a refrigeration system should be non-

toxic. However, all fluids other than air can be called as toxic as they will cause
suffocation when their concentration is large enough. Thus toxicity is a relative
term, which becomes meaningful only when the degree of concentration and time
of exposure required to produce harmful effects are specified. Some fluids are
toxic even in small concentrations. Some fluids are mildly toxic, i.e., they are
dangerous only when the concentration is large and duration of exposure is long.
Some refrigerants such as CFCs and HCFCs are non-toxic when mixed with air
in normal condition. However, when they come in contact with an open flame or
an electrical heating element, they decompose forming highly toxic elements (e.g.
phosgene-COCl2). In general the degree of hazard depends on:

- Amount of refrigerant used vs total space

- Type of occupancy
- Presence of open flames
- Odor of refrigerant, and
- Maintenance condition

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 Thus from toxicity point-of-view, the usefulness of a particular refrigerant
depends on the specific application.

e) Flammability: The refrigerants should preferably be non-flammable and non-

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

Based on the above criteria, ASHRAE has divided refrigerants into six safety
groups (A1 to A3 and B1 to B3). Refrigerants belonging to Group A1 (e.g. R11,
R12, R22, R134a, R744, R718) are least hazardous, while refrigerants belonging
to Group B3 (e.g. R1140) are most hazardous.

Other important properties are:

f) Chemical stability: The refrigerants should be chemically stable as long as they

are inside the refrigeration system.

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

metals)

h) Miscibility with lubricating oils: Oil separators have to be used if the refrigerant
is not miscible with lubricating oil (e.g. ammonia). Refrigerants that are
completely miscible with oils are easier to handle (e.g. R12). However, for
refrigerants with limited solubility (e.g. R 22) special precautions should be taken
while designing the system to ensure oil return to the compressor
i) Dilelectric strength: This is an important property for systems using hermetic
compressors. For these systems the refrigerants should have as high a dielectric
strength as possible

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

26.3.3. Economic properties:

The refrigerant used should preferably be inexpensive and easily

available.

26.4. Designation of refrigerants:

Figure 26.1 shows the classification of fluids used as refrigerants in vapour
compression refrigeration systems. Since a large number of refrigerants have
been developed over the years for a wide variety of applications, a numbering
system has been adopted to designate various refrigerants. From the number
one can get some useful information about the type of refrigerant, its chemical
composition, molecular weight etc. All the refrigerants are designated by R
followed by a unique number.

i) Fully saturated, halogenated compounds: These refrigerants are derivatives

of alkanes (CnH2n+2) such as methane (CH4), ethane (C2H6). These refrigerants
are designated by R XYZ, where:

X+1 indicates the number of Carbon (C) atoms

Y-1 indicates number of Hydrogen (H) atoms, and
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 Z indicates number of Fluorine (F) atoms

The balance indicates the number of Chlorine atoms. Only 2 digits indicates that
the value of X is zero.

Ex: R 22
X = 0 ⇒ No. of Carbon atoms = 0+1 = 1 ⇒ derivative of methane (CH4)
Y = 2 ⇒ No. of Hydrogen atoms = 2-1 = 1
Z = 2 ⇒ No. of Fluorine atoms = 2
The balance = 4 – no. of (H+F) atoms = 4-1-2 = 1 ⇒ No. of Chlorine atoms = 1
∴The chemical formula of R 22 = CHClF2

Similarly it can be shown that the chemical formula of:

R12 = CCl2F2
R134a = C2H2F4 (derivative of ethane)

(letter a stands for isomer, e.g. molecules having same chemical composition but
different atomic arrangement, e.g. R134 and R134a)

ii) Inorganic refrigerants: These are designated by number 7 followed by the

molecular weight of the refrigerant (rounded-off).

Ex.: Ammonia: Molecular weight is 17, ∴ the designation is R 717

Carbon dioxide: Molecular weight is 44, ∴ the designation is R 744
Water: Molecular weight is 18, ∴ the designation is R 718

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 Refrigerants

Pure fluids Mixtures

- Azeotropic
- Zeotropic

Synthetic Natural
- CFCs - Organic (HCs)
- HCFCs - Inorganic
- HFCs o NH3
o CO2
o H2O

Fig.26.1: Classification of fluids used as refrigerants

iii) Mixtures: Azeotropic mixtures are designated by 500 series, where as

zeotropic refrigerants (e.g. non-azeotropic mixtures) are designated by 400
series.

Azeotropic mixtures:

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

R 502: Mixture of R 22 (48.8 %) and R 115 (51.2%)
R503: Mixture of R 23 (40.1 %) and R 13 (59.9%)
R507A: Mixture of R 125 (50%) and R 143a (50%)

Zeotropic mixtures:

R404A : Mixture of R 125 (44%), R 143a (52%) and R 134a (4%)

R407A : Mixture of R 32 (20%), R 125 (40%) and R 134a (40%)
R407B : Mixture of R 32 (10%), R 125 (70%) and R 134a (20%)
R410A : Mixture of R 32 (50%) and R 125 (50%)

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iv) Hydrocarbons:

Propane (C3H8) : R 290

n-butane (C4H10) : R 600
iso-butane (C4H10) : R 600a

Unsaturated Hydrocarbons: R1150 (C2H4)

R1270 (C3H6)

26.5. Comparison between different refrigerants:

Synthetic refrigerants that were commonly used for refrigeration, cold storage
and air conditioning applications are: R 11 (CFC 11), R 12 (CFC 12), R 22
(HCFC 22), R 502 (CFC 12+HCFC 22) etc. However, these refrigerants have to
be phased out due to their Ozone Depletion Potential (ODP). The synthetic
replacements for the older refrigerants are: R-134a (HFC-134a) and blends of
HFCs. Generally, synthetic refrigerants are non-toxic and non-flammable.
However, compared to the natural refrigerants the synthetic refrigerants offer
lower performance and they also have higher Global Warming Potential (GWP).
As a result, the synthetic refrigerants face an uncertain future. The most
commonly used natural refrigerant is ammonia. This is also one of the oldest
known refrigerants. Ammonia has good thermodynamic, thermophysical and
environmental properties. However, it is toxic and is not compatible with some of
the common materials of construction such as copper, which somewhat restricts
its application. Other natural refrigerants that are being suggested are
hydrocarbons (HCs) and carbon di-oxide (R-744). Though these refrigerants
have some specific problems owing to their eco-friendliness, they are being
studied widely and are likely to play a prominent role in future.

Prior to the environmental issues of ozone layer depletion and global

warming, the most widely used refrigerants were: R 11, R 12, R 22, R 502 and
ammonia. Of these, R 11 was primarily used with centrifugal compressors in air
conditioning applications. R 12 was used primarily in small capacity refrigeration
and cold storage applications, while the other refrigerants were used in large
systems such as large air conditioning plants or cold storages. Among the
refrigerants used, except ammonia, all the other refrigerants are synthetic
refrigerants and are non-toxic and non-flammable. Though ammonia is toxic, it
has been very widely used due to its excellent thermodynamic and
thermophysical properties. The scenario changed completely after the discovery
of ozone layer depletion in 1974. The depletion of stratospheric ozone layer was
attributed to chlorine and bromine containing chemicals such as Halons, CFCs,
HCFCs etc. Since ozone layer depletion could lead to catastrophe on a global
level, it has been agreed by the global community to phase out the ozone
depleting substances (ODS). As a result except ammonia, all the other
refrigerants used in cold storages had to be phased-out and a search for suitable
replacements began in earnest. At the same time, it was also observed that in
addition to ozone layer depletion, most of the conventional synthetic refrigerants
also cause significant global warming. In view of the environmental problems
caused by the synthetic refrigerants, opinions differed on replacements for
conventional refrigerants. The alternate refrigerants can be classified into two
broad groups:
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 i) Non-ODS, synthetic refrigerants based on Hydro-Fluoro-Carbons
(HFCs) and their blends
ii) Natural refrigerants including ammonia, carbon dioxide, hydrocarbons
and their blends

It should be noted that the use of natural refrigerants such as carbon dioxide,
hydrocarbons is not a new phenomena, but is a revival of the once-used-and-
discarded technologies in a much better form. Since the natural refrigerants are
essentially making a comeback, one advantage of using them is that they are
familiar in terms of their strengths and weaknesses. Another important advantage
is that they are completely environment friendly, unlike the HFC based
refrigerants, which do have considerable global warming potential. The alternate
synthetic refrigerants are normally non-toxic and non-flammable. It is also
possible to use blends of various HFCs to obtain new refrigerant mixtures with
required properties to suit specific applications. However, most of these blends
are non-azeotropic in nature, as a result there could be significant temperature
glides during evaporation and condensation, and it is also important take
precautions to prevent leakage, as this will change the composition of the
mixture. Table 26.1 shows a list of refrigerants being replaced and their
replacements.

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 Refrigerant Application Substitute suggested
Retrofit(R)/New (N)
R 11(CFC) Large air conditioning systems R 123 (R,N)
o
NBP = 23.7 C Industrial heat pumps
R 141b (N)
hfg at NBP=182.5 kJ/kg As foam blowing agent
Tcr =197.98oC R 245fa (N)
Cp/Cv = 1.13
n-pentane (R,N)
ODP = 1.0
GWP = 3500
R 12 (CFC) Domestic refrigerators R 22 (R,N)
o
NBP = -29.8 C Small air conditioners R 134a (R,N)
hfg at NBP=165.8 kJ/kg Water coolers R 227ea (N)
Tcr =112.04oC Small cold storages R 401A,R 401B (R,N)
Cp/Cv = 1.126 R 411A,R 411B (R,N)
ODP = 1.0 R 717 (N)
GWP = 7300
R 22 (HCFC) Air conditioning systems R 410A, R 410B (N)
o
NBP = -40.8 C Cold storages R 417A (R,N)
hfg at NBP=233.2 kJ/kg R 407C (R,N)
Tcr =96.02oC R 507,R 507A (R,N)
Cp/Cv = 1.166 R 404A (R,N)
ODP = 0.05 R 717 (N)
GWP = 1500
R 134a (HFC) Used as replacement for R 12 No replacement required
o
NBP = -26.15 C in domestic refrigerators, water
hfg at NBP=222.5 kJ/kg coolers, automobile A/Cs etc * Immiscible in mineral oils
Tcr =101.06oC * Highly hygroscopic
Cp/Cv = 1.102
ODP = 0.0
GWP = 1200
R 717 (NH3) Cold storages No replacement required
o
NBP = -33.35 C Ice plants
hfg at NBP=1368.9 kJ/kg Food processing * Toxic and flammable
Tcr =133.0oC Frozen food cabinets * Incompatible with copper
Cp/Cv = 1.31 * Highly efficient
ODP = 0.0 * Inexpensive and available
GWP = 0.0
R 744 (CO2) Cold storages No replacement required
o
NBP = -78.4 C Air conditioning systems * Very low critical temperature
hfg at 40oC=321.3 kJ/kg Simultaneous cooling and * Eco-friendly
Tcr =31.1oC heating (Transcritical cycle) * Inexpensive and available
Cp/Cv = 1.3
ODP = 0.0
GWP = 1.0
Table 26.1: Refrigerants, their applications and substitutes

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 Refrigerant Application Substitute suggested
Retrofit(R)/New (N)
R718 (H2O) Absorption systems No replacement required
o
NBP = 100. C Steam jet systems * High NBP
hfg at NBP=2257.9 kJ/kg * High freezing point
Tcr =374.15oC * Large specific volume
Cp/Cv = 1.33 * Eco-friendly
ODP = 0.0 * Inexpensive and available
GWP = 1.0
R600a (iso-butane) Replacement for R 12 No replacement required
o
NBP = -11.73 C Domestic refrigerators * Flammable
hfg at NBP=367.7 kJ/kg Water coolers * Eco-friendly
Tcr =135.0oC
Cp/Cv = 1.086
ODP = 0.0
GWP = 3.0

Table 26.1: Refrigerants, their applications and substitutes (contd.)

Questions and answers:

1. Which of the following statements are TRUE?

a) A primary refrigerant does not undergo phase change in a refrigeration cycle

b) A secondary refrigerant does not undergo phase change in a refrigeration
cycle
c) The freezing point of a brine is generally lower than the freezing point of its
constituents
d) The freezing point of a brine is generally higher than the freezing point of its
constituents

Ans.: b) and c)

2. Which of the following statements are TRUE?

a) The suction pressure of a refrigerant should be as high as possible

b) The suction pressure of a refrigerant should be as low as possible
c) The discharge pressure of a refrigerant should be as high as possible
d) The discharge pressure of a refrigerant should be as low as possible

Ans.: a) and d)

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3. Which of the following statements are TRUE?

a) At a given temperature, as the latent heat of vaporization increases, the

saturation pressure decreases
b) For given evaporator and condenser temperatures, as the latent heat of
vaporization increases, the pressure ratio decreases
c) As the latent heat of vaporization increases, the required mass flow rate of
refrigerant, becomes smaller for a given capacity
d) For a given pressure ratio, as the isentropic index of compression increases,
the compressor discharge temperature increases

Ans.: a), c) and d)

4. Which of the following statements are TRUE?

a) A refrigerant having high critical temperature yields high COP and high
volumetric capacity
b) A refrigerant having high critical temperature yields low COP and high
volumetric capacity
c) A refrigerant having high critical temperature yields low COP and low
volumetric capacity
d) A refrigerant having high critical temperature yields high COP and low
volumetric capacity

Ans.: d)

5. Which of the following statements are TRUE?

a) Low molecular weight refrigerants have high latent heat of vaporization

b) Low molecular weight refrigerants have low latent heat of vaporization
c) For saturated state at the inlet to the compressor, a refrigerant having high
vapour specific heat may give rise to wet compression
d) For saturated state at the inlet to the compressor, a refrigerant having low
vapour specific heat may give rise to wet compression

Ans.: a) and c)

6. The chemical formula of refrigerant R11 is:

a) CCl3F
b) CClF3
c) CClHF
d)CHF

Ans.: a)

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7. The chemical formula of R141 is:

a) C2H3ClF3
b) C2H2Cl3F
c) C2H3Cl2F
d) C2H2ClF3

Ans.: c)

8. Which of the following statements is TRUE?

a) Evaporation process is non-isothermal for zeotropic mixtures

b) Evaporation process is non-isothermal for azeotropic mixtures
c) Composition of azeotropic mixture changes in the event of a leak
d) Composition of zeotropic mixture changes in the event of a leak

Ans.: a) and d)

9. Which of the following refrigerants are phased-out due to Montreal protocol on

ozone layer depletion

a) R11
b) R21
c) R12
d) R32

Ans.: a), b) and c)

10. Which of the following refrigerants replace R12 in domestic refrigerators?

a) R22
b) R11
c) R134a
d) R141b

Ans.: c)

11. Which of the following refrigerants are suggested as replacements for R22 in
large air conditioning and cold storage systems?

a) R134a
b) R21
c) R410A
d) R407C

Ans.: c) and d)

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