DEPARTMENT OF ELECTROMECHANICAL ENGINEERING

INSTITUTE OF TECHNOLOGY
HAWASSA UNIVERSITY

Refrigeration and Air Conditioning - MEng 5202

Part 1 – Refrigeration
1.2. Refrigerants

By: Million M.
Mr. Million M., Thermal Engineer, Hawassa
12/19/2023 1
University
 Refrigerants
• Refrigerants are specially selected substances which acts as a cooling agent by
absorbing heat from another body or substance in refrigerators and air conditioners.

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Refrigerants Generations
• The historic progression of refrigerants encompasses four phases based on defining
selection criteria

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First generation – whatever worked (1830-1930)

• The first generation of refrigerants constitute the most common refrigerants for the
first 100 years.

• They effectively including whatever worked and was available.

• Nearly all of these early refrigerants were flammable, toxic, or both, and some were
also highly reactive. Accidents were common.

• At first the only practical fluids were carbon dioxide, ammonia and Methyl chloride.

 Ammonia was unsuitable owing to its toxic nature.

 Methyl chloride, toxic and very unpleasant although it was used in some smaller systems.
 Carbon dioxide, require much higher pressures system.

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Second generation – safety and durability (1931-1990)

• The second generation was distinguished by the invention and the shift to
fluorochemicals for safety and durability.

• The chlorofluorocarbons (CFCs) together with hydrochlorofluorocarbons (HCFCs)

became the definitive refrigerants and dominated the second generation of
refrigerants.

• The CFC family refrigerant seemed to possess the desirable properties like non-toxic,
and non-flammable, good thermodynamic properties and oil miscibility characteristics.

• They enabled the expansion of refrigeration into the commercial, domestic and air
conditioning sectors.

• Carbon dioxide was eclipsed, but ammonia with its excellent thermodynamic
properties and low cost continued to be applied in many industrial applications.

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 When chlorine and bromine
Third generation – ozone protection (1990-2010) atoms come into contact with
ozone in the stratosphere, they
destroy ozone molecules

• Environmental concerns of ozone depletion, Linked with CFC refrigerants catalyzed the
third generation with focus on stratospheric ozone protection.

• The Vienna Convention and resulting Montreal Protocol(1987) an international treaty forced
abandonment of ozone‐depleting substances (ODSs).

• The ozone depleting CFC refrigerants will be phased out by 2030 as per the decision of the
Montreal protocol, with emphasis on HCFCs for transitional use and hydrofluorocarbons
(HFCs) for the longer term.

• The production of CFC refrigerants ended in 1996 in developed countries and in 2010 in
developing countries, under the Montreal Protocol

• The replacement chlorine-free HFCs were developed and have been successfully applied in
almost all applications and successfully countered ozone depletion.

• In addition, the shifts also sparked renewed interest in ‘‘natural refrigerants’’ particularly
ammonia, carbon dioxide, hydrocarbons, and water – along with expanded use of
absorption

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Fourth generation – global warming (2010-)
• A very successful response to ozone depletion stands however, The HFCs are powerful
greenhouse gases, resulting deteriorating situation with climate change (global warming).

• The Kyoto Protocol(Signed, 1997, become Effective, 2005), was created in response to concerns
surrounding climate change. The treat was an agreement between developed nations to
reduce carbon dioxide emissions and greenhouse gases (methane, nitrous oxide and
fluorinated gases).
• Some of the most damaging HFCs, including R404A, are destined to be phased out

• This has speeded the development of a new class of hydrofluoroolefin (HFO) refrigerants.

• HFOs, with a short atmospheric life, have extremely low global warming impact but there
are flammability and cost issues.

• European F-Gas regulations (compliance with the Montreal Protocol) are a set of rules adopted by the
European Union to control the emissions of fluorinated greenhouse gases (F-gases) (include hydrofluorocarbons
(HFCs)), which are man-made gases used in various industrial applications and have a high global warming
potential. The main objectives are to:
 Limit the total amount of F-gases that can be sold in the EU and phase them down in steps to one-
fifth of 2014 sales in 2030 and complete phase out by 2050.

 Ban the use of F-gases in some new types of equipment where less harmful alternatives are
available, such as domestic refrigerators, supermarket refrigeration, air conditioning, foams, and
inhalers 7
• The ozone depletion potential (ODP) of a refrigerant represents its effect on atmospheric
ozone, and the reference point usually adopted is ODP = 1 for the CFC R11

• The global warming potential (GWP) of a gas is a rating based on the warming effect
of a substance’s warming effect compared to the warming effect of carbon dioxide. .

 The refrigerant only affects global warming directly if it is released into the atmosphere.

For example: R134a has a GWP of 1300, which means

that the emission of 1 kg of R134a is equivalent to
1300 kg of CO2.

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 Classification Of Refrigerants

Primary Refrigerants Secondary Refrigerants

• Primary refrigerants are those working mediums or • Secondary refrigerants are those circulating
heat carries which directly take part in the substances which are first cooled with the help of
refrigeration system The primary refrigerants and are then employed
for cooling purposes.
• They cool the substance by the absorption of latent
heat (with a change of phase) • These refrigerants cool substances by absorption
of their sensible heat (without a change of phase).
Examples, Ammonia, Carbondioride, Sulphur dioxide,
Methyl chloride, Methylene chloride, Ethyl chloride and Examples water, brines, glycols, etc.
Freon group etc.
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Halocarbon compounds
• These refrigerants are derived by replacing one or more hydrogen atoms in a hydrocarbon
molecule such as ethane or methane with one or more of the three halogens - chlorine, fluorine,
and bromine.

• Halocarbon compounds, commercially popular as Freon, Genetron, Isotron and Areton, etc.

• The halocarbon family is comprised of refrigerants which are non-flammable and most of them
are non-toxic too.

• A group of refrigerants in which the chlorine atoms are

replaced by bromine atoms Like R13B1 are known as halons.
Chlorofluorocarbons (CFC's)
• Chlorofluorocarbons (CFC's) refrigerant is composed of Chlorine, Flourine, Carbon.

• CFC refrigerants have a high ODP and are on of the major causes of ozone depletion.

HCFC refrigerants
• Hydrochlorofluorocarbons (HCFC’s) are composed of: Hydrogen, Chlorine, Fluorine, Carbon

• HCFC refrigerant and refrigerant blends tends to break down in the lower atmosphere and cause less
ozone depletion than CFC’s.

• HCFC’s linger in the atmosphere for a long time and have a high GWP.

HFC refrigerants
• Hydrofluorocarbons (HFC’s) are refrigerants that contain: Hydrogen, Fluorine, Carbon and do not have
chlorine atoms.

• HFC’s are considered to have a 0 ODP but, some HFC’s have a high GWP

HFO refrigerants
• Hydrofluoro-olefin is a new category of refrigerants, they contain: Hydrogen, Fluorine, Carbon
• HFO’s have 0 ODP and lower GWP values.
• HFO’s are beginning to be used in automotive air conditioning. The two most popular HFO’s are:
 HFO-1234yf - low-GWP replacement for R- 134a in automotive
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 HFO-1234ze - to replace R-410a in residential and light commercial air conditioning and heat pump
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Hydrocarbons
• Hydrocarbons are organic compounds that contain carbon and hydrogen.

• These substances are the components in petroleum and natural gas.

• Most of this equipment includes:

 Stand-alone retail refrigerators
 Freezers
 Domestic refrigerators and freezers

• These refrigerants have the desired thermodynamics properties, but are highly flammable.

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Inorganic compounds
• Before the introduction of hydrocarbon group these refrigerants were most commonly used for
all purposes.

Unsaturated organic compound

• The refrigerants belonging to this group possess ethylene or propylene as their constituents.

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Refrigerant Blends And Glide

• Refrigerant blends contain a mixture of two or more refrigerants. That are being
developed to strengthen or compensate for certain properties.

• Generally, a refrigerant blend that contain two refrigerants is called Binary

refrigerants. If it contains three refrigerants, the term for that is a ternary blend.

• Many of the HFC and HFO refrigerants are blends of two or more individual chemicals.

• Mixtures can be Azeotropes, Near Azeotropes or Zeotropes.

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Azeotropes Blends (refrigerant) -R500 series

 is a mixture of two or more components that boil at the same temperature that are
different from those of its constituents i.e. exhibit a single boiling point, at one particular
pressure.

 An azeotrope evaporates and condenses as a single substance. i.e. even though there are
different refrigerants inside, they change states at the same quantity (do not undergo
any separation).

 They possess fixed thermodynamic properties

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Zeotropic (Non Azeotropes ) blends - R400 series

 is a mixture of two or more components which have different boiling point at a given
pressure.

 The different individual refrigerant boil/condense over a range of temperatures instead of

just one temperature. They can’t be defined by a single pressure-temperature
relationship.

 The difference between Lowest individual saturation to the Highest individual saturation
temperature is called Temperature Glide (Glide)
 The temperature at which Evaporation starts (the saturated liquid temperature) is called
the bubble point

 The temperature at which condensation starts (the saturated vapor temperature) is called
the dew point

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 Notice that: during phase change process change in composition of a blend may occur (more of
one component will transfer to the other phase faster than the rest) This property is called
fractionation.

 Consider the following vapour compression cycle with R407C (R32,

R125 and R134a). Constant P1, evaporating, and P2 condensing
pressure

Condensation

 The temperature at which condensation starts is called the dew

point, denoted here as T2 (dew) corresponds to a temperature of
approximately 40°C

 As condensation progresses, the temperature falls to T2 (bubble)

corresponds to a bubble point temperature of approximately 34°C.

Evaporation

 The temperature during the evaporation process changes from T1

(evaporator inlet) to T1 (dew), as the lighter components of the
mixture, R32 and R125, evaporate preferentially to the R134a.

 The remaining liquid becomes R134a rich, its boiling point gradually
increasing until all the liquid is evaporated.

R-32, is flammable, the overall mixture composition is not flammable

R-407C has 7.2 ° C glide temperature
R407 R32 221.44 -51.71
A long-term, non-ozone depleting replacement for R-22
R125 224.59 -48.56
Used in various air-conditioning applications
R134a 247 -26.15
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• Near Azeotropes Blends are mixtures which exhibit a glide of less than 2K.

 For practical purposes they may be treated as single substances.

 Examples are R404A and R410A.

 The following recommendations apply to the use of blends:

 Equipment must always be charged from the liquid phase, or the component concentrations
will be incorrect.

 Ingress of air must be avoided.

 Never attempt to make your own mixture of refrigerants. Azeotropic and zeotropic are
patented refrigerants and the manufacturing process is complicated.

 Blends which have a large temperature glide, greater than 5K, should not be used with
flooded-type evaporators.

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• The safety classification of refrigerants is based on the combination of toxicity and
flammability: A1, A2, A3, B1, B2, and B3.

 R-134a and R-22 are in the A1 group, lower toxicity and nonflammable;
 R-123 in the B1 group, higher toxicity and nonflammable; and
 R-717 (ammonia) in the B2 group, higher toxicity and lower flammability.

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Desirable Properties Of Refrigerants
• Ideal properties for a refrigerant listed as follows:
 High latent heat of vaporization
 Low viscosity
 High suction gas density
 Positive but not excessive pressures at evaporating and condensing conditions
 Critical temperature and triple point well outside the working range
 Chemically stable,
 Compatible with construction materials
 Miscible with lubricants
 Non-corrosive, non-toxic, odorless and non-flammable
 High dielectric strength
 Environmentally friendly, Zero ODP and zero GWP
 Low cost

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Thermodynamic properties

Boiling temperature: The boiling temperature of the refrigerant at atmospheric pressure should be
low, if the boiling temperature of the refrigerant is high, the compressor should be operated at high
vacuum and the operating cost will be on the higher side.

Freezing temperature: The freezing temperature of a refrigerant should be well below the operating
evaporator temperature

Evaporator and condenser pressure: Both evaporator and condenser pressure should be positive (i.e
above atmosphere)

Latent heat of vaporization A refrigerant should have a high latent of evaporation at the evaporator
temperature. The high latent heat results in high refrigerating effect per kg of refrigerant circulated
which reduces the mass of refrigerant to be circulated per tonne of refrigerant

Critical temperature and pressure: The critical temperature of refrigerant is the highest temperature
at which it can be condensed to a liquid, regardless of a higher pressure the critical temperature
should be higher than condensing temperature that might be encountered

Specific volume: The specific volume of the refrigerant vapour at evaporator temperature (volume of
suction vapour to the compressor) indicates the theoretical displacement of the compressor 24
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Chemical properties of refrigerants

Flammability: Hydro carbon refrigerant are highly flammable.

Ammonia is also somewhat flammable and becomes explosive when mixed with air.
Halocarbon refrigerants are neither flammable nor explosive

Toxicity: All fluorocarbon refrigerants mix with certain percentage of air become toxic

Miscibility: The ability of a refrigerant to mix with oil is called miscibility. The degree of miscibility
depends on the temperature of the oil and pressure of the refrigerant vapour.

Effect on perishable materials: The refrigerant used in cold storage plant and in domestic
refrigerators should be such that in case of leakage, it should have no effect on the perishable
materials.

The Freon group of refrigerant have no effect upon dairy products, meats vegetables, flowers.
There will be no charge in color exposed to freon.

Ammonia may react with fruits and vegetables which are acidic in nature.
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Physical properties of refrigerants

Stability: An ideal refrigerant should not decompose at any temperature normally encountered in
the refrigeration system.

Corrosive: The corrosive property should be taken in to account while selecting the refrigerant.
The freon group of refrigerants are non corrosive with all metals practically.
Where as Ammonia is used with iron or steel.

Viscosity: The refrigerant in the liquid and vapor states should have low viscosity. The heat transfer
through condenser and evaporator is improved at low viscosity.

Thermal conductivity: The refrigerant in the liquid and vapor states should have high thermal
conductivity.

Cost and leakage tendency: The cost of refrigerant is also important for industrial and commercial
refrigerating system

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Designation Of Refrigerants
 Fully saturated, halogenated compounds: The general formula applies:

𝐶𝑚 𝐻𝑛 𝐶𝑙𝑝 𝐹𝑞 in which 𝑛 + 𝑝 + 𝑞 = 2𝑚 + 2.

m = the number of carbon atoms

n = the number of hydrogen atoms
p = the number of chlorine atoms
q = the number of fluorine atoms

• The numbers of the various refrigerants types are of the three-digit variety and are written in the
form 𝑹 − 𝑿𝒀𝒁, where:

𝑋 =𝑚−1 It is however omitted if it is equal to zero (for the methane derivatives).

𝑌 =𝑛+1
𝑍 =𝑞
• The chemical formula for any compound derived from a hydrocarbon is denoted by

𝑅 − ( 𝑚 − 1) (𝑛 + 1) (𝑞) 29
Example: Calculate the chemical formula of refrigerant R134:
According to the above mentioned convention:
No. of C atoms: C – 1 = 1 => C = 2
No. of H atoms: H + 1 = 3 => H = 2
No. of F atoms: F = 4
No. of Cl atoms: Cl = 0
The compound is C2H2F4 and its name is Tetra‐fluoro‐ethane

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 A suffix with a lower case letter such as a, b, or c indicate an isomer(two or more
compounds with the same formula but have a different arrangement of atoms)

 A suffix with an uppercase letter such as A, B, or C indicate the different percentages of

refrigerants that are blended together.

 The designation of the cyclic hydrocarbons is the same as above except that a C is placed in
front of the nomenclature number.

 Unsaturated organic compounds are designated by putting an additional number 1

before the refrigerant.

Example: R120 = C2H4Cl3, i.e. Trichloroethylene but is designated as R1120

 Inorganic refrigerants: These are designated by number 7 followed by the molecular weight
of the refrigerant (rounded‐off). (are in the 700 series.)

Example: Ammonia: Molecular weight is 17, the designation is R 717

Carbon dioxide: Molecular weight is 44, the designation is R 744
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Water: Molecular weight is 18, the designation is R 718
 Miscellaneous organic compounds are in the 600 series; numbers are given in numerical
order,

Example R600a, isobutane

 The brominated refrigerants are denoted by putting an additional B and a number to

denote as to how many chlorine atoms are replaced by bromine atoms.

Example: R13B1 is derived from R 13 with the replacement of one chlorine atom by a bromine atom. Its
chemical formula is therefore CF3Br.

 Blends are designated by their respective refrigerant numbers and weight proportions.
Refrigerants are named in order of increasing normal boiling points of the components.

Zeotropic mixtures are assigned an identifying number in the 400 series. This number
designates which components are in the mixture and the following upper-case letter
denotes the proportions.

Azeotropic blends are assigned an identifying number in the 500 series. It is not necessary
to cite the percentages of weight in parentheses here.

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Common Refrigerants

• Developments and environmental considerations could

 Further restrict the use of HFCs in the future,
 Develop a share for HFOs and
 Increase the share of the so-called natural refrigerants.

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 Mr. Million M., Thermal Engineer, Hawassa
12/19/2023 38
University
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