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What is a Refrigerant
• 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 R22 in
vapour compression and Ammonia in vapour
absorption refrigeration systems.
• Primary refrigerants fluids provide refrigeration by
undergoing a phase change process in the
• 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
What are Chlorofluorocarbons (CFCs)?
These are substances containing Chlorine, Fluorine and
Carbon. Also classified as Halocarbons, ie compounds that
contain atoms of carbon and halogen atoms. The following are
some CFC refrigerants with their chemical composition:
• R11 (CCl3F)
• R12 (CCl2F2) Dichlorodifluoromethane
• R13 (CClF3)
• R113 (CCl2FCClF2);
• R114 (CClF2CClF2);
• R115 (CF3CClF2);
CFCs are now totally banned from use or production
within all countries covered by the Montreal Protocol.
What are Hydro Chlorofluorocarbons (HCFCs)?
These are substances containing Hydrogen, Chlorine,
Fluorine and Carbon. HCFCs have replaced CFCs as
refrigerants, being less harmful to the environment .
The following are some HCFC Refrigerants with their
chemical composition :
• R22 (CHClF2) Chlorodifluoromethane
• R31 (CH2ClF2)
• R123 (CF3CHCl2)
• R124 (CHClFCF3)
HCFC gases were banned in Jan 2010. General phase out in
developed countries was completed by end 2015.
What are Hydrofluorocarbons (HFCs)?

Hydrofluorocarbons (HFCs) are substances containing hydrogen,

fluorine and carbon. They are generally colourless and odourless
gases and are mostly chemically un-reactive. The following are
some HFC Refrigerants with their chemical composition :
• R23 (CHF3)
• R32 (CF2H2)
• R134a (CF3CFH2) Tetrafluoroethane,
• R125 (CF3 CHF2)
• R143a (CF3CH3)
• R410 (a 1:1 zeotropic mixture of R32 and R125 )
• In order to identify groups of refrigerants, a numbering
system was devised. A refrigerant was indicated with ‘R’
followed by a unique number (thus Freon-12 is changed to
R12 etc). The numbering of refrigerants was done based on
certain guidelines.
• For all synthetic (man made) refrigerants the number (e.g.
11, 12, 22) denotes the chemical composition.
• The number of all inorganic refrigerants begins with ‘7’
followed by their molecular weight. Thus R-717 denotes
ammonia (ammonia is inorganic and its molecular weight is
17), R-718 denotes water etc..
• Refrigerant mixtures begin with the number 4 (zeotropic) or 5
(azeotropic), e.g. R-500, R-502 etc.
What is Ozone Layer
• Ozone is an isotope of oxygen with three atoms instead
of two. It is a naturally occurring gas which is created by
high energy radiation from the Sun.
• The greatest concentration of ozone is found from 12 km
to 50 km above the earth forming a layer in the
stratosphere which is called the ozone layer.
• This layer, which forms a semi-permeable blanket,
protects the earth by reducing the intensity of harmful
ultra-violet (UV) radiation from the sun.
• Fluorocarbons migrate to the upper atmosphere and are
broken by the intense solar radiation and release chlorine
atoms responsible for ozone depletion
Harmful Consequences of Ozone Depletion
For Humans. Increase in
• Skin cancer
• Snow blindness
• Cataracts
Less immunity to
• Infectious diseases
• Malaria
• Herpes
For plants
• Smaller size
• Lower yield
• Increased toxicity
• Altered form

• Signed in 1987 under the United Nations Environment

Program (UNEP). 197 countries have ratified as of Dec
• Pakistan ratified the Montreal Protocol and the London
Amendment on 18 December 1992, the Copenhagen
Amendment on 17 February 1995 and the Montreal and
Beijing Amendments on 2 September 2005.
• Pakistan is classified as a Party operating under
paragraph 1 of Article 5 of the Protocol.
• One of most successful examples of international
cooperation in UN history
Montréal Protocol - Control Schedule

Ozone depleting Developed countries Developing countries

CFCs phased out end of 1995 total phase out by 2010

Halons phased out end of 1993 total phase out by 2010

HCFCs total phase out by 2020 total phase out by 2040

Environmental and safety properties
The important environmental and safety properties are:
a) Ozone Depletion Potential (ODP): According to the
Montreal Protocol, the ODP of refrigerants should be zero,
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). CFC 11 is taken as datum ie ODP = 1.0

b) Since ODP depends on the presence of chlorine or bromine,

refrigerants having either chlorine (i.e., CFCs and HCFCs) or
bromine cannot be used under the new regulations
Freon Group Refrigerants Application and ODP Values
Refrigerant Areas of Application ODP
CFC 11(R11) Air-conditioning Systems ranging from 200 to 2000 1.0
(As datum) tons capacity. It was used where low freezing
point and non-corrosive properties were important.

CFC 12 ( R12 ) Used for most applications, ie air-conditioning 1.0

plants, refrigerators, freezers, ice-cream cabinets,
water coolers, window air-conditioners, automobile
air conditioners.

CFC 13 (R13) For very low temp refrigeration up to –90C in 1.0

cascade system

CFC113 ( R113 ) Small to medium air-conditioning systems and 1.07

industrial cooling

CFC114 ( R114 ) In household refrigerators and in large industrial 0.8


R502 (Blend of Frozen food ice-cream display cases and ware-

R22 and R115) houses and food freezing plants. An excellent 0.34
general low temp refrigerant
Environmental Effects of Refrigerants

Global warming :
• Refrigerants directly contributing to global warming
when released to the atmosphere

• Indirect contribution based on the energy

consumption of among others the compressors if
electrically driven ( CO2 produced by power stations )
Environmental and safety properties
• 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. Carbon Dioxide with GWP = 1 is
taken as datum.
• 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. Refrigerants with a low
a value of TEWI are preferable from global warming point
of view.
Environmental and safety properties
• Toxicity: Ideally, refrigerants should be non-toxic.
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
• Some fluids are mildly toxic, i.e., they are dangerous
only when the concentration is large and duration of
exposure is long. 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
Environmental and Safety Properties
of Refrigerants

• Flammability: The refrigerants should preferably be

non-flammable and non-explosive.
• Chemical stability: The refrigerants should be
chemically stable as long as they are inside the
refrigeration system.
• Compatibility : With common materials of
construction, both metals and non-metals.
Environmental and safety properties
• Miscibility with lubricating oils: Oil separators are
used if the refrigerant is not miscible with lubricating
oil (e.g. ammonia). Refrigerants like R12 that are
completely miscible with oils are easier to handle.
• Ease of leak detection: In the event of leakage of
refrigerant from the system, it should be easy to
detect the leaks.
• Economic properties: The refrigerant used should
preferably be inexpensive and easily available.



R22,R124 R134a,R152a NH3, HC'S
(Refrigerant Emissions and Leakage Zero) Project
• The Regulations aim to improve containment of HFC
refrigerants through leak testing, engineer
qualification and record keeping.
• The Institute of Refrigeration has provided practical
information to help industry comply with the F-Gas
Regulation and make a real reduction in refrigerant
• This has been achieved mainly through the REAL Zero
(Refrigerant Emissions And Leakage Zero) project.
Halocarbon Refrigerants
Halocarbon Refrigerants are all synthetically produced and
were developed as the Freon family of refrigerants. CFC
refrigerants leaked during the manufacturing and normal
operation or at the time of servicing or repair, mix with
surrounding air and rise to troposphere and then into
stratosphere due to normal winds or storms. The Ultraviolet
rays act on CFC and release Chlorine atoms.
Examples :
– CFC’s : R11, R12, R113, R114, R115
– HCFC’s : R22, R123
– HFC’s : R134a, R404a, R407C, R410a
• Remain a popular choice
– especially for R22 phase out
• Good efforts at reducing leakage e.g. REAL
Zero project
• Interest in R407A to replace R404A
– 50% reduction in GWP
• Transitional compounds with low ODP
• Partially halogenated compounds of
• Remaining hydrogen atom allows Hydrolysis
and can be absorbed.
• R22, R123
• Production frozen at 1996 level
• 35% cut by 2005, 65% by 2010
• 90% by 2015, 100 % by 2020
• 20 year grace period for developing countries.
R22 (HCFC)
• ODP = 0.055, GWP = 1700
• R22 has 40% more refrigerating capacity
• Higher pressure and discharge temp and not
suitable for low temp application
• Extensively used in commercial air-
conditioning and frozen food storage and
display cases
R123 (HCFC)
• ODP = 0.02, GWP = 90
• As a replacement for R11 as it has similar
thermo-dynamic properties.
• Very short atmospheric life but classified as
• Retrofit alternative to R11
• Zero ODP as it has no chlorine atom; contains
only Hydrogen and Fluorine
• High GWP values in some cases
• No phase out date in Montreal Protocol
• R134a and R152a – Very popular refrigerants
• HFC refrigerants are costly.
R134a (HFC)
• ODP-0, GWP-1300
• Used as a substitute for R12 and to a limited
range for R22
• Good performance in medium and high temp
• Toxicity is very low
• Not miscible with mineral oil
R152a (HFC)
• ODP=0, GWP= 140
• R152a is another attractive HFC with similar
properties to R12.
• GWP is one order less than HFC 134a but it is
slightly flammable.
• Also it has lower energy consumption. Hence
the Environmental Protection Agency of
Europe prefers HFC 152a to HFC 134a
Hydrocarbon Refrigerants
• Very promising non-halogenated organic
• With no ODP and very small GWP values
• Their efficiency is slightly better than other
leading alternative refrigerants
• They are fully compatible with lubricating oils
conventionally used with R12.
Hydrocarbon Refrigerants
• Extraordinary reliability - The most convincing
argument is the reliability of the hydrocarbon system
because of fewer compressor failures.
• But most of the hydrocarbons are highly flammable
and require additional safety precautions during use as
• Virtually no refrigerant losses
• Hydrocarbons have been used since the beginning of
the century and now being considered as long term
solutions to environmental problems.
Sec B 14 Jun 17
Hydrocarbon Refrigerants
• Dominant in domestic market like household
refrigerators and freezers
• Growing use in very small commercial systems like
car air-conditioning systems
• Examples: R170, Ethane, C2H6
R290 , Propane C3H8
R600, Butane, C4H10
R600a, Isobutane, C4H10
Blends of the above Gases
Approximate auto ignition temperatures
• R22 6300 C
• R12 7500 C
• R134a 7400 C
• R290 4650 C
• R600a 4700 C
Azeotropic Refrigerants
• A stable mixture of two or more refrigerants that
boils at a constant characteristic temperature lower
or higher than any of its components and that
retains the same composition in the vapor state as
in the liquid state.
Examples : R-500 : 73.8% R12 and 26.2% R152
R-502 : 48.8% R22 and 51.2% R115
R-503 : 40.1% R23 and 59.9% R13
Zeotropic Refrigerants
• A zeotropic or non-azeotropic mixture is one whose
composition in liquid phase differs to that in vapour
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%)
R410a : R32/125 (50%, 50%)
R413a : R600a/218/134a (3%, 9%, 88%)
Inorganic Refrigerants
• Carbon Dioxide
• Water
• Ammonia
• Air
• Sulphur dioxide
Carbon Dioxide
• Zero ODP, GWP = 1
• Non Flammable, Non toxic
• Inexpensive and widely available
• Its high operating pressure provides for system size
and weight reducing potential.
• Drawbacks:
• Operating pressure (high side) : 80 bars
• Low efficiency
Ammonia – A Natural Refrigerant
Ammonia is produced in a natural way by
human beings and animals; 17 grams/day for

Natural production 3000 million tons/year

Production in factories 120 million tons/year

Used in refrigeration 6 million tons/year

Ammonia as Refrigerant
• Zero ODP & GWP
• Excellent thermodynamic characteristics: small
molecular mass, large latent heat, large vapour
density and excellent heat transfer characteristics
• High critical temperature (132oC) : highly efficient
cycles at high condensing temperatures
• Its smell causes leaks to be detected and fixed before
reaching dangerous concentration
• Relatively low price
Some Drawbacks of Ammonia as
• Toxic
• Flammable ( 16 – 28% concentration )
• Not compatible with copper
• Temperature on discharge side of
compressor is higher compared to other
Water (R-718)
• Zero ODP & GWP
• Water as refrigerant is used in absorption
system. New developing technology has
created space for its use in compression
cycles also.
• But higher than normal working pressure
in the system can be a factor in restricting
its use as a refrigerant
Application of New Eco-friendly Refrigerants
Application HFCs used Possible Eco-friendly refrigerant
Domestic refrigeration R134a,R152a HC600a and blends
Commercial refrigeration R134a,R404A,R407C HC blends, NH3, CO2
Cold storage, food R134a,R404A, NH3, CO2 HCs
processing and industrial R507A
Unitary air conditioners R410A,R407C CO2 , HC s
Centralized AC (chillers) R134a,R410A,R407C NH3, CO2 HCs, water
Transport refrigeration R134a,R404A CO 2,
Mobile air conditioner R134a CO2 ,HCs
Heat pumps R134a,R152a,R404A NH3, HCs, CO2, water
R407C, R410A

Sec A 13 Jun 13
Survey of Refrigerants
Refrigerant Group Atmospheric ODP GWP
R11 CFC 130 1 4000
R12 CFC 130 1 8500
R22 HCFC 15 .055 1700
R134a HFC 16 0 1300
R404a HFC 16 0 3260
R410a HFC 16 0 1720
R507 HFC 130 1 3300
R717 NH3 - 0 0
R744 CO2 - 0 1
R290 HC <1 0 8
R600a HC <1 0 8
• In the aftermath of the Montreal protocol HFCs have
predominantly replaced CFCs and HCFCs in RAC
• Due to their high GWP, HFCs are not a good
replacement solution.
• The solution lies with natural refrigerants :
Ammonia, Hydrocarbons and Carbon dioxide
• Systems need to have low TEWI factor
• High efficiency with ammonia and lower power
consumption with hydrocarbons
• Sec D 14 Jun 17, Sec C 15 Jun 17 Sec A 19 Jun 17 Sec B 20 jun