M4 Unit 1

Introduction to Refrigerants

Prof Md Razali bin Ayob

24hb Januari 2011

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 Learning Outcomes
• At the end of this lecture, the students should be able to:-

– Define what is refrigerant and its relation to the industrial

development

– Itemise various types of refrigerant available in the market

– Discuss the classification of refrigerant in terms according to its

distinct feature and application

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 Content
1. Introduction
2. Types of Refrigerant
3. Classification of Refrigerants
4. Refrigerant Numbering
5. Conclusion

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 1. Introduction
• Refrigerant is any body or substance that acts as a cooling agent by
absorbing heat from another body or substance. Absorbtion of heat
heat through vaporization or expansion processes.

• ASHRAE Standard 34-1978

– It is a medium of heat transfer in a refrigerating system which
picks up heat by evaporating at low temperature and pressure
and gives up heat on condensing at a higher temperature and
pressure

• Evaporating and condensing of a medium involves phase change

• Refrigerants are fluids that absorb heat at low temperatures and

rejects heat at higher temperatures

• Note: ASHRAE = American Society of Heating, Refrigerating and Air Conditioning Engineers
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• It is understood that Refrigeration is the cooling of substances below
ambient temperatures by extracting heat from them.

• The medium that absorbs the heat from the substance to be cooled
is called the refrigerant.

• Refrigerants can be classified into two main groups:

– First: absorb heat by undergoing a change of state (for example from liquid to
vapor)
– Second: absorb heat without undergoing a change of state (for example they
may absorb heat as a liquid and remain a liquid, albeit a hotter one).

• If the refrigerant is only used to transport "cold" from one place to

another it is called a secondary refrigerant.

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• Substance should possess certain chemical, physical and
thermodynamic properties as well as safe and economic to use.

• Sold in disposable container that include a check valve - limits the

reuse of old refrigerants and prevents mixing refrigerants.

• Refrigerants are identified by a standard colour code and labels that

contain information on which type of refrigerant is in the container
along with any safety hazards.

• Common examples of cooling medium:

– Cold water, brine solution, anti-freeze

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 2. Types of Refrigerant
Commonly divided into:
1. Primary
– Pass through evaporating and condensing cycle e.g. Ammonia,
‘Freon’ group
2. Secondary
- Transfer heat from remote point to the evaporator of the
refrigeration system e.g. calcium chloride

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 Common Refrigerants
Air: completely nontoxic, free but low coefficient of performance.

Ammonia: one of the oldest, widely used (commercial and industrial),

flammable and highly toxic

Carbon Dioxide: colorless and odorless gas, heavier than air,

nontoxic and nonflammable but need high operating pressures.
Usedin marine refrigeration, theatre air conditioning systems and
hotel refrigeration systems.

Freon Refrigerants: man-made, ethane and methane as bases,

widely used but now being phase-out

No substance has claimed to be an ideal working refrigerants for all

operating conditions.

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• Anhydrous ammonia is the most common refrigerant used in
industrial refrigeration today; often referred to as R-717, ammonia,
or NH3.

• The application of ammonia to refrigeration systems has become

universally known as the field of industrial refrigeration.

• Ammonia has the distinct advantage:

– high latent heat and
– excellent heat transfer properties.

• Ammonia is also readily available at an economical cost when

compared to other commercial refrigerants.

• From an environmental viewpoint, ammonia has no ozone depletion

or global warming potential and is biodegradable.

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• Carbon dioxide (CO2 or R744) has been extensively used in the
past.

• It is undergoing a popular resurgence and has distinct advantages

for low temperature applications.

• One of the benefits of using CO2 in low temperature refrigeration

system is the low specific volume of the refrigerant vapor.

• Hence small compressor displacement (ft 3/min or m3/min), help to

reduce the installed size of the compressor(s).

• CO2 is also considered a high-pressure refrigerant.

• The use of CO2 as a refrigerant does not contribute to the

greenhouse gas problem as this is simply recovered gas from the
atmosphere.

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• Propane (R-290) or Propylene (R-1270) are two other examples of
common refrigerants known as hydrocarbons.

• Commonly found in large chemical processing or refinery facilities.

• While propane and propylene are suitable as refrigerants they are

also flammable gases.

• This restricts their use to facilities where the requirements of specific

area classifications such as explosion proof electrical devices are
common place.

• Criteria to chose refrigerants may include:

– safety considerations, operating temperatures, familiarity with the refrigerant and
its specific requirements, or ease of integration into existing infrastructure.

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 Common elements that form refrigerants. Nitrogen and hydrogen formed ammonia, NH 3

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 3. Classification of Refrigerants
Based on the following consideration:
a) Application
b) Chemical composition
c) Safety
d) Hazard to Life

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 a) Application
• Temperature based
– Very low: - 160 oC to – 273 oC (113 K – 0 K) Cryogenics
– Medium (- 40 to 0 oC) and Normal (0 oC and above)
• Brine: ice making system
• Anti-freezant: glycerine, glycols and methyl alcohol when mixed with
water produces temperature up to – 40 oC
• Absorbent in vapour absroption refrigeration system: utilised to
create cooling effect by creating low boiling points of refrigerant by
absorbing them due to their high affinity, e.g. ammonia and water;
Lithium bromide and water
• Vapour compression refrigeration system: involved phase change
from liquid to vapour

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 b) Chemical Composition

Refrigerant
Cyclic
Methane
Series e.
Ethane Propane
Organic
Zeotropic Azeotropic Organ Unsaturat Inorganic
Series series Blends (3 s (2 ed Compou
(R-10 to Compou refrigerant refigerants ic Organic
R-50
(R-110 (R-216 –
nd (C- s blended, blended, Compoun
nd (R-
(methane to R-170 R-290
316 to C- different same Comp d (R-1112 702 to R-
) ethane) propane) 318) properties) properties) ound to R-1270) 764)

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 Cont.
Hydrocarbon or Halocarbon family of compound
– Based on methane (CH4) and ethane (C2H6)
– Methane and ethane are pure hydrocarbon

– Contained Fl, Cl and Br

– e.g. some famous one,
• R11 trichloromonofluoromethane CCl3F
• R12 dichlorofluoromethane CCl2F2
• R22 monofluorodifluoromethane CHClF2

– Synthesis by replacing one or more hydrogen atoms (H2) in

methane (CH4) or ethane (C2H6) molecules

• Take away one or more hydrogen atoms and replacing with atoms of
24hbchlorine Cl2, fluorine F and bromine
Januari 2011 Br, form halogen family
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 Cont…
– Contains organic compounds, use in many industrials
installation, flammable, satisfactory thermodynamic
properties
– Some famous one:
• Methane CH4 R50 m.w. 16
• Ethane CH3CH3 R170 30
• Propane CH3CH2CH3 R290 44
• Butane CH3CH2CH2CH3 R600 58
• Ethyl ether C2H2OC2H5 R610 74
• Methyl amine CH3NH2 R630 31

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 Cont..
• ChloroFluoroCarbon (CFCs)
– contain chlorine, fluorine and carbon
– carry high amounts of chlorine so they are known for being the
most hazardous to the ozone layer

• Hydrogenated ChloroFluoroCarbon (HCFCs)

– made up of hydrogen, chlorine, fluorine, and carbon
– these refrigerants contain minimal amounts of chlorine; they are
not as detrimental to the environment as some other refrigerants

• HydrogenatedFluoroCarbon (HFCs)
– made up of hydrogen, fluorine, and carbon
– known to be one of the least damaging to our ozone because they
do not use a chlorine atom (which is used in most refrigerants)
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 Cont….
• Azetropes
– Mixture of two refrigerants which do not separate into their
compounds with pressure or temperature, have fixes
thermodynamics properties, e.g.
– Has common blending properties

No. Comp. Formula M.W.

500 R12 + R512a (73+27) CCl2F2/CH3CHF2 99.3
502 R22 + R115 (49+51) CHClF2/CClF2CF3 111.6
503 R23 + R13 (40+60) CHF3/CCLF3 87.5
504 R32 + R115 (48+52) CHF2/CClF2CF3 78.2

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 Cont..
• Zeotropes
– Mixture of three common refrigerants
– Maintain individual refrigerant properties
– Indicated by number 400
– Blends of:
• HCFC and HFC
• HCFC, HC and HFC

– Some famous one

• R402a HCFC/HC/HFC R125/290/22 60/2/38
• R404A HFC R125/143a/134a 44/52/4

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 Cont…..
• Inorganic compounds
– Early refrigerants in used
– E.g. Ammonia NH3R717 m.w. 17
water H 2O R718 18
air 29
Carbon dioxide CO2 R744 44
Sulphur dioxide SO2 R764 64

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 c) Safety
• Two issues:
– Toxicity and Flammability
• Type of Toxicity
– Chronic and acute
• Chronic toxicity: long term exposures over a lifetime of experience
with refrigeration equipment
• Acute toxicity: dangers posed by short-term exposure to very high
concentration of refrigerant or during very brief but intense
exposure that service personnel may accidently experience during
repairs.

• Safe if refrigerant stays contained in the cylinder or in the system

• Hazard occurs when the refrigerant comes out of the container or
system, often quickly and unexpectedly. Need regular safety checks

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• Toxicity and personal exposure

• Most refrigerants have undergone extensive toxicity testing

• involves a range of exposure levels and
• times to determine any possible effects on test animals.
• Short term exposures at high concentrations indicate any acute
hazards such as irritation, sensitization of the heart or adrenaline
and lethal concentration
• LC50 is the amount which kills half the animals in a short amount of
time.
• Tests that expose animals for longer periods of time, such as 90
days to two years, are designed to indicate chronic problems.
• include mutagenicity (changes to cells), reproductive problemss
• effects on organs or carcinogenicity (cancer-causing).

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 Cont.
• National Refrigeration Safety Code US

– Group I: Safe
• E.g. R11, R12, R113, R744, R502

– Group II: Toxic and somewhat inflammable

• E.g. R40, R160, R717, R764

– Group III: Inflammable

• E.g. R170, R290, R600, R1150

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 Cont..
• ASHRAE Standard 34-1992

– Toxicity
• A: relatively low toxicity with threshold limit value (TLV) of 400
ppm or more
• B: higher toxicity with TLV less than 400 ppm

– Flammability
• Class 1: compounds are not flammable (no flame propagation)
• Class 2: relatively low flammability
• Class 3: high flammability

ppm = parts per million

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• ASHRAE Standard 34* provides a safety classification for refrigerants
based on information related to personal exposure.

• ASHRAE Standard 15** uses this safety rating and additional toxicity
information to set requirements for machinery rooms and sets limits on
the amount of refrigerant allowed in systems outside machinery rooms.

• Exposure levels: values given to refrigerants to indicate how much of

the chemical a person can regularly be exposed to without adverse
effects.

* ANSI/ASHRAE Standard 15, "Safety Code for Mechanical Refrigeration," American Society of Heating, Refrigerating and Air
Conditioning Engineers Inc., Atlanta.
** ANSI/ASHRAE Standard 34, "Designation and Safety Classification of Refrigerants," American Society of Heating, Refrigerating, and
Air Conditioning Engineers Inc., Atlanta.

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• The American Conference of Government and Industrial Hygienists
(ACGIH) sets the TLV-TWA values for chemicals.

• TLV-TWA stands for Threshold Limit Value-Time Weighted Average,

which is the amount of chemical a person can be exposed to for 8
hours a day, 40 hours a week, without adverse effects.

• The reference point for enthalpy uses the ASHRAE standard of

-40°F (-40°C). Do not mix data from different sources as each
source may use a different reference point.

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• The maximum value for any chemical is 1,000 ppm, due to safety
reason, hence low value
• General rules to follow are:
– Minimize the amount of refrigerant released.
– Proper recovery procedures, including clearing hoses, will keep the refrigerant in
the containers instead of potentially exposing it to people.
– Never intentionally release refrigerant in a confined space. Even the safest
refrigerant can still displace enough oxygen to cause suffocation.
– Set up ventilation equipment, like a portable fan, in areas where possible release
would mean high concentrations.
• If someone is exposed to refrigerant get him to fresh air, give
oxygen if needed, and get him checked by a doctor.

• Other organisations and toxicity indexes:

– Workplace Environmental Exposure Limit (WEEL) set by the American Industrial
Hygiene Association (AIHA)
– Permissible Exposure Limit (PEL) set by OSHA
– Acceptable Exposure Limit (AEL) used by DuPont.

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• Flammable refrigerants present an immediate danger when released into
the air.

• Refrigerant can combine with air at atmospheric pressure and ignite,

causing a flame and possibly an explosion to occur.

• Use of flammable refrigerants is restricted to controlled environments

that have monitors, proper ventilation, explosion-proof equipment and
generally few people near the equipment (refineries, storage
warehouses, breweries, etc.).

• Some refrigerants can burn with oxygen, but only at higher pressures or
temperatures and never in air at atmospheric conditions.
– Nickname as "combustible" refrigerants.
– Underwriter's Laboratories (UL) lists these refrigerants as "Practically Nonflammable.“
– E.g. R22, R134a

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• R-22 was found to cause a combustion hazard during a pressurized
leak test with air.
– Hence most refrigerants should be used only with pressurized nitrogen for leak
testing
• Minimum ventilation required: 1 cfm/sq.ft.

• Recommended ventilation: 2 cfm/sq.ft or 12 air changes per hour -

half the air supplied and exhausted near the ceiling and half the air
supplied and exhausted near the floor

• Decomposed or burned refrigerant will form acids products

– Hydrochloric acid (HCI), if the refrigerant contains chlorine
– hydrofluoric acid (HF), if it contains fluorine.

• These products are formed when hydrogen is present such as from

the breakdown of oil, water or if the refrigerant has hydrogen
attached (like R-22 or R-134a).
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• If oxygen also is present (from air or water), it's possible to form
carbon monoxide, carbon dioxide and various unsaturated carbonyl
compounds -- the most notorious of which is phosgene.

• Phosgene contains two chlorine atoms and an oxygen atom.

• It will only form when oxygen is present and only the refrigerants
with chlorine attached will produce phosgene (not HFCs).

• R22 has only one chlorine atom per molecule, so it is extremely

difficult, chemically speaking, to get another one attached to form
phosgene.

• Decomposition of R-22 or HFCs may form other carbonyl fluorides,

however they are not as toxic as phosgene.

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 Refrigerant leak detection
• Refrigerant leaks detection:
– Common: electronic sniffers, bubble tests, halide torches, fluorescent dyes and
water immersion
– New: infrared, ultrasonic and advanced heated diode detectors

• Infrared (IR) leak detectors:

– Humidity, smoke, air flow or temperature changes won’t hinder detection speed
and accuracy.
– longer life, providing low overall cost

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• Ultrasonic leak detectors:
– sensitive to hissing sounds associated with gas leaks, although they aren’t gas
specific
– can filter out background noise
– Leaks from high-pressure fittings cause greater turbulence, easier to locate –
even if the source is outside the line of sight.
– High-quality headphones are recommended to make the most of this technology.
– Some machine sensitive to sounds around 40 kHz (twice the highest frequency
the best human hearing can detect)
– can filter out wind noise, voices, traffic and most normal operational sounds.

• Probability source of leaks:

– a failed connection, seal or component could enter an occupied area.

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 Cont…
Low toxicity High toxicity
TLV >400ppm TLV<400 ppm

No flame propagation A1 B1
(most of commercial (R123)
refrigerants e.g.
R134a, R22, R502)
Low flammability A2 B2
(R152a, R142a) (R717 ammonia)

High flammability A3 B3
(R290, propane) (vinyl chloride)

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 Safety Matrix

Refrigerant safety classifications from ASHRAE Standard 34.

[13] © James M. Calm, 1992.
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Carbon atom all over (flammable)
+ Carbon = hydrocarbon, e.g. R30, R31, R32, R40, R41, R50

No chlorine atom, no effect on ozone layer

(toxic)
Chlorine + Fluorine + Carbon = CFC

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 d) Hazard to Life
• Introduced by Under Writers Laboratory of USA

• Group from 1 to 6 with decreasing order of seriousness

– 1 = lethal or produce serious injury e.g. SO2
– 6 = expose up to 2 hours, do not produce injury e.g. R12

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 4. Refrigerant Numbering
Series Compounds/type
000 Methane based
100 Ethane based
200 Propane based
300 Cyclic organic
400 Zeotropes
500 Azetropes
600 Organic compounds
700 Inorganic compounds
1000 Unsaturated inorganic compounds

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 Hydrocarbons and derivatives
• The first digit on the right (units) is the number of fluorine (F) atoms.

• The second digit on the right (tens) is one more than the number of
hydrogen (H) atoms.

• The third digit on the right (hundreds) is one less than the number of
carbon (C) atoms (when the digit is zero, it is omitted from the
number).

• The fourth digit on the right (thousands) is equal to the number of

unsaturated carbon-carbon bonds (when the digit is zero, it is
omitted from the number).

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 Cont.
• For refrigerants that contain bromine (Br), the letter B is added after
the identification number, followed by the number of atoms present.
(note: no longer manufactured in developed countries)

• The number of chlorine (Cl) atoms is found by subtracting the sum

of fluorine, bromide, and hydrogen atoms from the total number of
atoms that can be connected to the carbon atoms: 4 for methane
derivatives (CH4), 6 for ethane derivatives (C2H6),

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 Cont..
• Example:
– R22 (chlorodifluoromethane – CHClF2)

• R022
– 2: Number of fluorine atoms (F=2)
– 2: Number of hydrogen atoms + 1 (H=1+1)
– 0: Number of carbon atoms – 1 (C=1-1)
– 1: Number of chlorine atoms : 1 (Cl=4-1-2)
(i.e. 4 minus 1 hydrogen atom and minus 2 fluorine atoms)

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 Cont…
• For cyclic derivatives, the letter C is used before the refrigerant’s
identification number.
– Example: RC318 (octafluorocyclobutane – C4F8)

• In the case of isomers in the ethane series, each has the same number,
with the most symmetrical one indicated by the number alone.

• As the isomers become more and more unsymmetrical, successive

lowercase letters (i.e. a, b or c) are appended.
– Example: R134 and R134a

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 Refrigerant Blending

• Blends break down into two types:

– Zeotropes and Azeotropes
• Zeotrope refrigerant
– mixes are mainly made of three different types of refrigerants
– Characteristic: this type of refrigerant is that all three refrigerants keep
their own properties
– they act as 3 individual refrigerants.
• Azeotrope refrigerant
– mainly a blend of two refrigerants
– Property: this type of refrigerant is it acts as a single refrigerant
– Thus effect the boiling points of both types of refrigerants.
• Mixtures are designated by their respective refrigerant numbers and
mass proportions
• Refrigerants shall be named in order of increasing normal boiling
points of the components.

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 R-4xx & R-5xx series
• Zeotropic mixtures shall be assigned an identifying number in the
400 series.

• To differentiate among zeotropes having the same components with

different amounts (percent by mass), an uppercase letter shall be
added as a suffix.
– Example: R407A (R32/R125/R134a (20/40/40))
R407B (R32/R125/R134a (10/70/20))
R407C (R32/R125/R134a (23/25/52))
R407D (R32/R125/R134a (15/15/70))
R407E (R32/R125/R134a (25/15/60))

• Azeotropic mixtures shall be assigned an identifying number in the

500 series.
– Example: R507 (R125/R143a (50/50))

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 R-6xx and R-7xx Series
• Miscellaneous organic compounds shall be assigned a number in
the 600 series; numbers are given in numerical order.
– Example: R600a, isobutane

• Inorganic compounds
– Inorganic compounds shall be assigned a number in the 700
series, identification numbers are formed by adding the relative
molecular mass of components to 700.
– Example: R717 corresponds to ammonia which has a molecular
mass of 17.

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 Thank You

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