Introduction To Refrigerants - : in This Lecture

ME340A: Prof.
Sameer Khandekar
http://home.iitk.ac.in/~samkhan
ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Instructor: Prof. Sameer Khandekar Indian Institute of Technology Kanpur
Tel: 7038; e-mail: samkhan@iitk.ac.in Kanpur 208016 India
Introduction to
Refrigerants
– Part I
Sameer Khandekar
Sameer Khandekar
Sir M. Visvesvaraya Chair Professor
Department of Mechanical Engineering
Indian Institute of Technology Kanpur
Kanpur (UP) 208016 INDIA
Webpage: home.iitk.ac.in/~samkhan/ 1

In this lecture…
◉ Importance of selection of suitable refrigerant.
◉ Classification of refrigerants into primary and secondary.
◉ Important differences between primary and secondary
refrigerants.
◉ Refrigerant selection criteria based on thermodynamic,
thermophysical, environmental and economic properties.
◉ Numbering system used for designating refrigerants.
Sameer Khandekar
◉ Comparison between different refrigerants.

208016 Kanpur India 1
ME340A: Prof. Sameer Khandekar

1 Introduction
What are refrigerants?
Sameer Khandekar

Introduction
◉ Refrigerant : is the primary working fluid used for absorbing and

transmitting heat in a refrigeration system.
◉ In principle, any fluid can be used as a refrigerant.
◉ Refrigerants absorb heat at low temperature and low pressure and
release heat at a higher temperature and pressure
◉ Typically, refrigerants undergo phase-changes during heat
absorption (evaporation) and heat releasing (condensation)
Sameer Khandekar
◉ Air used in an air-cycle refrigeration system can also be considered

as a refrigerant (no phase-change).
◉ We will focus on those fluids that can be used as refrigerants in
VCR systems only.
4


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,
Sameer Khandekar
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.
5

Introduction
◉ 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.
Sameer Khandekar


Primary and Secondary

2 Refrigerants
Importance, use, differences…
Sameer Khandekar

Primary and secondary refrigerants
◉ Primary refrigerants are those fluids, which are used directly as

working fluids, for example in VCR and absorption based systems.
◉ These fluids provide the necessary refrigeration by undergoing a

phase-change process in the evaporator, absorbing latent heat.
◉ As the name implies, secondary refrigerants are those liquids,

which are used for transporting thermal energy from one location
to other.
Sameer Khandekar
◉ Secondary refrigerants are also known referred to as brines or anti-

freezes.
8


◉ If the operating temperatures are above 0°C, then pure water can
also be used as secondary refrigerant, for example in large air
conditioning systems (like we have in IIT Kanpur).
◉ Antifreezes or brines are used when refrigeration is required at

sub-zero temperatures.
◉ Unlike primary refrigerants, secondary refrigerants do not undergo

phase change as they transport energy from one location to other.
Sameer Khandekar

Primary and secondary refrigerants/ Cooling Medium
◉ Secondary refrigerants are also called as Cooling medium.
◉ Cooling Medium: is a working fluid cooled by the refrigerant to

transport the cooling effect between a central plant and remote
cooling units and terminals
◉ Chilled water, brine, and glycol are used as cooling media in many
refrigeration systems.
Sameer Khandekar
◉ It reduces the extensive circulation of the primary refrigerant.
10


◉ 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 (i.e. mixture components).
◉ The temperature at which freezing of a brine takes place depends

on its concentration. The concentration at which a lowest
temperature can be reached without solidification is called as
eutectic point.
Sameer Khandekar
◉ 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.
11

History of refrigeration
◉ 1830s - Jacob Perkins - Vapor Compression (ether) Main challenges

◉ 1851 - John Gorrie - Patent for Air Cycle
• Low Toxicity
◉ 1859 - R-717 / R-718 (Ammonia / Water) • Non-flammable
• Good Stability
◉ 1866 - CO2 - Marine Applications
• Atmospheric Boiling Point
◉ 1873 - R-717 (Ammonia) Commercial Refrigeration between -40°C and 0°C
◉ 1875 - R-764 (Sulfur dioxide)

◉ 1920s -R-600a (Isobutane) & R-290 (Propane)
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◉ 1922 - Willis Carrier - R-1130 (Dielene)

◉ 1926 - R-30 (Methylene Chloride)
12


Common refrigerants in 1920-30
◉ Ammonia (R-717) NH3

◉ Carbon Dioxide CO2
◉ Sulfur Dioxide SO2
◉ Hydrocarbons CnHm
◉ Methyl Choride CH3Cl Use of Synthetic Refrigerants:
◉ Water H2O (Stability, non-toxicity and efficiency)
Sameer Khandekar
• 1930: R11, R12

• 1936: R22
• 1961: R507
13

Classes of refrigerants
Organic: Some examples
◉ Hydro-carbons HC (natural starting molecules
from which most refrigerants are synthesized)
○ Methane (R-50) and Ethane (R-170)
◉ Chloro-Flouro Carbons (CFC)
◉ Hydro Chloro-Flouro Carbons (HCFC)
◉ Hydro-Fluoro Carbons (HFC)
In-organic: Some examples
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◉ Water
◉ Ammonia Refrigerants can also be
◉ CO2 mixed with each other
14


Historical perspective
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15

Refrigerant consumption in developing countries (2015)

Sameer Khandekar
16


Hydrocarbon refrigerants
◉ Many hydrocarbon gases have successfully been used as

refrigerants in industrial, commercial and domestic
applications.
◉ Examples:
○ R170, Ethane, C2H6
○ R290 , Propane C3H3
○ R600, Butane, C4H10
○ R600a, Isobutane, C4H10
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○ Blends of the above gases
17

Halocarbons
◉ Halocarbon refrigerants are all synthetically produced and

were developed as the FREON family of refrigerants.
◉ Examples :
○ CFC’s : R11, R12, R113, R114, R115
○ HCFC’s : R22, R123
○ HFC’s : R134a, R404a, R407c, R410a
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18


Molecular structures of common refrigerants

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19

Property trends/ H-Cl-F

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20


Blending of refrigerants
◉ Two or more refrigerants can be suitably blended to achieve

the required/desired properties
○ Flammability
○ Volumetric Capacity
○ Limit discharge superheating for lower discharge Temp
◉ Two Basic Types
○ Zeotropes
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○ Azeotropes
21

Thermodynamics of mixtures
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22


Thermodynamics of mixtures
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23

Azeotropic refrigerants
◉ A stable mixture of two or several refrigerants whose vapor

and liquid phases retain identical compositions over a wide
range of temperatures.
◉ Examples:
○ R-500: 73.8% R12 and 26.2% R152
○ R-502: 8.8% R22 and 51.2% R115
○
Sameer Khandekar
R-503: 40.1% R23 and 59.9% R13
24


Zeotropic refrigerants
◉ A zeotropic mixture is one whose composition in liquid phase differs to that
in vapor phase. Zeotropic refrigerants therefore do not boil at constant
temperatures unlike azeotropic refrigerants.
◉ Examples:
○ R404a : R125/143a/134a (44%,52%,4%)
○ R407c : R32/125/134a (23%, 25%, 52%)

Sameer Khandekar
○ R410a : R32/125 (50%, 50%)
○ R413a : R600a/218/134a (3%, 9%, 88%)

25

3 Properties of Refrigerants
Desirable thermophysical properties…
Sameer Khandekar
26


Essential properties of refrigerants
◉ Latent heat of vaporization is one of the most important properties.
◉ Chemical stability under conditions of use is another equally

important characteristics.
◉ Safety codes may require a non-flammable refrigerant of low

toxicity for most applications.
◉ Cost, availability, efficiency, and compatibility with compressor

Sameer Khandekar
lubricants and materials with which the equipment is constructed.
27

Physical properties
◉ The refrigerants are arranged in

increasing order of atmospheric
boiling point, from air at
-194.3°C to water at 100°C
◉ Normal boiling point is most
important because it is a direct
indicator of the temperature
level at which a refrigerant can
Sameer Khandekar
be used.
28


Refrigerant selection criteria
◉ Selection of refrigerant for a particular application is based on the

following requirements:
○ Thermodynamic and thermo-physical properties.
○ Environmental and safety properties, like:
■ Ozone depletion potential (ODP), global warming potential

(GWP), and combustibility
Sameer Khandekar
■ Economics of production/maintenance/etc.
29

Thermodynamic and thermo-physical properties
◉ Suction pressure: At a given evaporator temperature, the saturation

pressure should be above atmospheric for prevention of air or
moisture and non-condensable gases ingress into the system and
ease of leak detection. Higher suction pressure is better as it leads
to smaller compressor displacement
◉ Discharge pressure: At a given condenser temperature, the

discharge pressure should be as small as possible to allow light-
weight construction of compressor, condenser, pipe, etc.
Sameer Khandekar
30


◉ Pressure ratio or Compression ratio: Should be as small as possible

for high volumetric efficiency and low power consumption
◉ Latent heat of vaporization: Should be as large as possible so that
the required mass flow rate per unit cooling capacity will be small
◉ From the above equation, it can be seen that for given condenser
Sameer Khandekar
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. 31


◉ Isentropic index of compression: Should be as small as possible so
that the temperature rise during compression will be small.
◉ Liquid specific heat: Should be small so that degree of subcooling
will be large leading to smaller amount of flash at evaporator inlet.
◉ Vapor specific heat: Should be large so that the degree of
superheating will be small.
◉ Thermal conductivity: Thermal conductivity in both liquid as well
Sameer Khandekar
as vapor phase should be high for higher heat transfer coefficients.

◉ Viscosity: Viscosity should be small in both liquid and vapor phases
for smaller frictional pressure drops.
32


Environmental and safety properties
◉ In contemporary times, environment friendliness of the refrigerant

is a major factor in deciding its usage.
◉ 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. R11, R12) or will be in near-future (e.g. R22).
Sameer Khandekar
◉ 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.
33

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

a GWP value as possible to minimize global warming.
◉ Refrigerants with zero ODP but a high value of GWP (e.g. R134a)
are likely to be regulated in future.
◉ 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.
Sameer Khandekar
◉ Naturally, refrigerants with as a low a value of TEWI are preferable

from global warming point of view.
34


◉ 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.
◉ Hence, 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.
Sameer Khandekar
◉ 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.
35

◉ 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
Sameer Khandekar
○ Presence of open flames

○ Odor of refrigerant, and
○ Maintenance condition
36


◉ 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
Sameer Khandekar
to Group B3 (e.g. R1140) are most hazardous.

◉ Finally, economic properties: The refrigerant used should
preferably be inexpensive and easily available.
37

Comparison/ Issues
Sameer Khandekar
38


Nomenclature of
4 Refrigerants
How to name them?
Sameer Khandekar
39

Designation of refrigerants/ Nomenclature
◉ 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
Sameer Khandekar
number.
40


ASHRAE Standards (Number 34)
◉ The number assigned to each refrigerant is related to its chemical

composition and the system has been formalized as ASHRAE
Standard 34. Broadly, the numbering system is as follows:
○ 000 Series Methane Based
○ 100 Series Ethane Based
○ 200 Series Propane Based
○ 300 Series Cyclic Organic Compounds
○ 400 Series Zeotropes
○
Sameer Khandekar
500 Series Azeotropes

○ 600 Series Organic Compounds
○ 700 Series Inorganic Compounds
○ 1000 Series Unsaturated Organic Compounds
41

Designation of refrigerants/ Nomenclature

1. Fully saturated, halogenated compounds:
◉ These refrigerants are derivatives of alkanes (CnH2n+2) such as
methane (CH4), ethane (C2H6) and propane (C2H8).
◉ 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
○ Z indicates number of Fluorine (F) atoms
Sameer Khandekar
○ The balance indicates the number of Chlorine atoms.
◉ Only 2 digits indicates that the value of X is zero.
42


Nomenclature: Example
Example: 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
Sameer Khandekar
■ 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)
43

Isomeric refrigerants
2,3,3,3-Tetrafluoropropene, HFO-
1234yf, is a hydro-fluoro-olefin (HFO)
with the formula CH2=CFCF3.
This molecule can have several

isomers
NEW CLASS OF REFRIGERANT

Sameer Khandekar
44


Examples
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45

Nomenclature
2. 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-718ide
Sameer Khandekar
◉ Sulpher dioxide:
◉ Air
46


Complete Nomenclature explained
◉ The first digit on the right is the number of fluorine (F) atoms.
◉ The second digit from the right is one more than the number of
hydrogen (H) atoms.
◉ The third digit from the right is one less than the number of carbon
(C) atoms. When this digit is zero it is omitted from the number.
◉ The fourth digit from the right is equal to the number of

Sameer Khandekar
unsaturated carbon-carbon bonds in the compound. When this

digit is zero, it is omitted from the number.
47

Complete nomenclature explained
◉ The number of chlorine (Cl) atoms is found by subtracting the sum

of the flourine (F), bromine (Br - if present) and hydrogen (H)
atoms from the total number that can be attached to carbon. With
one carbon, the total number of attached atoms is four. With two
carbons, the total number is six and with three carbons, the total
number is eight.
◉ In some cases, part or all of the chlorine atoms are replaced with
bromine and the letter B is used in the number. The number
Sameer Khandekar
following the letter B shows the number of bromine atoms present.
48


◉ Blends are designated by their respective refrigerant numbers and

weight proportions. rest of text okay, add this. To differentiate
among blends having same components with different proportions,
an uppercase letter shall be added to designation. For example, R-
402A and R-402B.
◉ Zeotropic blends that have been commercialized shall be assigned

an identifying number in the 400 series. This number designates
which components are in the mixture but not the amount of each.
Sameer Khandekar
The amount of each component is designated as described in 7

above. For example the 60/40 weight % mixture of R-12 and R-114
would be R-400 (60/40).
49

◉ Azeotropic compounds that have been commercialized shall be

assigned an identifying number in the 500 series. It is not necessary to
cite the percentages parenthetically once a 500 series is assigned.
◉ The 600 series has been assigned to miscellaneous organic compounds.
Within the organic 600 series, the assignments are serial.
◉ The 700 series has been assigned to inorganic compounds with relative
molecular masses less than 100. Within the 700 series, the relative
molecular mass of the compounds is added to 700 to arrive at the
Sameer Khandekar
identifying refrigerant numbers. When two or more inorganic

refrigerants have the same relative molecular masses, uppercase letters
(i.e., A, B, C, etc.) are added to distinguish among them.
◉ The 1000 series has been assigned to unsaturated organic compounds. 50


Thanks!
Any questions ?
You can write to me
◉ samkhan@iitk.ac.in
Sameer Khandekar
51


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ME340A: Prof.

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ Comparison between different refrigerants.

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ Refrigerant : is the primary working fluid used for absorbing and

◉ Air used in an air-cycle refrigeration system can also be considered

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ The thermodynamic efficiency of a refrigeration system depends

global warming and their relation to the various refrigerants used,

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ Replacement of an existing refrigerant by a completely new

◉ Hence, it is very important to understand the issues related to

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Primary and Secondary

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Primary and secondary refrigerants

◉ Primary refrigerants are those fluids, which are used directly as

◉ These fluids provide the necessary refrigeration by undergoing a

◉ As the name implies, secondary refrigerants are those liquids,

◉ Secondary refrigerants are also known referred to as brines or anti-

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Primary and secondary refrigerants

◉ Antifreezes or brines are used when refrigeration is required at

◉ Unlike primary refrigerants, secondary refrigerants do not undergo

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Primary and secondary refrigerants/ Cooling Medium

◉ Secondary refrigerants are also called as Cooling medium.

◉ Cooling Medium: is a working fluid cooled by the refrigerant to

◉ It reduces the extensive circulation of the primary refrigerant.

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Primary and secondary refrigerants

◉ An important property of a secondary refrigerant is its freezing

◉ The temperature at which freezing of a brine takes place depends

◉ The commonly used secondary refrigerants are the solutions of

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ 1830s - Jacob Perkins - Vapor Compression (ether) Main challenges

◉ 1875 - R-764 (Sulfur dioxide)

◉ 1922 - Willis Carrier - R-1130 (Dielene)

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Common refrigerants in 1920-30

◉ Ammonia (R-717) NH3

• 1930: R11, R12

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

Refrigerant consumption in developing countries (2015)

Department of Mechanical Engineering

ME340A: Refrigeration and Air Conditioning Department of Mechanical Engineering

◉ Many hydrocarbon gases have successfully been used as