CHEMICAL PROCESS UTILITY

Refrigerants and Refrigeration

Prof. Shishir Sinha
DEPARTMENT OF CHEMICAL ENGINEERING

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 Topics to be covered?
o Introduction to Refrigerants
o Classification of refrigerants
✓ Halocarbons
✓ Hydrocarbons
✓ Inorganic compounds
✓ Azeotropic mixtures
✓ Non-azeotropic mixtures
o Prefix and coding for refrigerants
o Isomers
o Introduction to refrigeration and it’s history

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 Introduction to Refrigerants
Refrigerants
o Refrigerants are well known as fluids absorbing heat during
evaporation, and which provide a cooling effect during the phase
change form liquid to vapor, are commonly used in refrigeration, air
conditioning, heat pump system and in process system.

e.g., ammonia (R-717), Carbon dioxide (R-744),

Ethyl chloride (R-160), isobutane (R-600a), methyl
chloride (R-40), methylene chloride (R-30) and
sulfur dioxide (R-764), and CFCs.

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Classification of Refrigerants
The primary refrigerants can be classified into the following five
main groups;
1. Halocarbons
2. Hydrocarbons
3. Inorganic compounds
4. Azeotropic mixture
5. Non-azeotropic mixtures

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1. Halocarbons
The halocarbons contain one or more of the three halogens chlorine,
fluorine, or bromine and are widely used in refrigeration and air
conditioning systems as refrigerants.
They are commonly known by their trade names such as Freon,
Arcton, Genetron, Isotron and Uron.
In this group, the halocarbons, consisting of
chlorine, fluorine, and carbon, have been the
most commonly used refrigerants (so-called
chlorofluorocarbons, CFCs).

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Cont…
o CFCs have been commonly used as refrigerants, solvents, and foam
blowing agents such as the most common CFCs have been CFC-11
or R-l 1, CFC-12 or R-12, CFC-113 or R-l 13, CFC-114 or R-l 14 and
CFC-115 or R-115.
o CFCs are odorless and nontoxic and heavier than air, as well as
dangerous if not handled properly.

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Cont…

o Inhalation of high concentrations is not detectable by human

senses and can prove fatal due to oxygen exclusion caused by CFC
leakages in an enclosed area.
o The combustion products of CFCs includes, phosgene, hydrogen
fluoride and hydrogen chloride, which are highly poisonous if
inhaled.

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o There are some other components such as halons, carbon
tetrachlorides and perfluorocarbons.
o Halons are compounds consisting of bromine, fluorine and carbons,
the halons (halon 1301, 1211) are used as fire extinguishing agents,
both in built-in systems and in hand held portable fire
extinguishers.

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o Carbon tetrachloride (CCl4) was widely used as a raw materials
in many industrial uses, including production of CFCs and found
carcinogenic.
o Perfluorocarbons (PFC) have an extremely high effect on global
climate change and very long lifetimes, have impact on global
warming.

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2. Hydrocarbons
o Hydrocarbons (HCs) are the compounds that mainly consists of
carbon and hydrogen. HCs include methane, ethane, propane,
cyclopropane, butane, and cyclopentane.
o Although HCs are highly flammable, they may
offer advantages as alternative refrigerants
because they are inexpensive to produce and
they have zero ozone depletion potential, very
low global warming potential, and low toxicity.

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Types of Hydrocarbons
o Hydrobromofluorocarbons (HBFCs) are the compounds that consist
of hydrogen, bromine, fluorine, and carbon.
o Hydrochlorofluorocarbons (HCFCs) are the compounds that consist
of hydrogen, chlorine, fluorine, and carbon. They can deplete ozone
but in lesser extent then CFCs, having potential ranging from 0.01 to
0.1.

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o Hydrofluorocarbons (HFCs) are the compounds that consist of
hydrogen, fluorine, and carbon. They Can be used as
replacements for CFCs because don’t contain chlorine, bromine
and don’t deplete the ozone layer and have depletion potential
of zero.

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Cont…
o Methyl bromide (CH3Br) is a compound consisting of carbon,
hydrogen, and bromine. It is an effective pesticide and used to
fumigate soil and many agricultural products and have depletion
potential of 0.6.
o Methyl chloroform (CH3Cl) is a compound
consisting of carbon, hydrogen, and chlorine.
Methyl chloroform is used as an industrial
solvent. Its ozone depletion potential is 0.11.

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Note:
o For refrigeration applications, a number of hydrocarbons such as
methane (R-50), ethane (R-170), propane (R-290), n-butane (R-
600), and isobutane (R-600a) that are suitable as refrigerants can
be used.

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3. Inorganic compounds
o In spite of early invention of inorganic compounds, today they are
still used in many refrigeration, air conditioning and heat pump
applications as refrigerants e.g., ammonia (NH3), water (H2O), air,
carbon dioxide and sulfur dioxide (SO2).

Note:
Here, in this study we have focused on three
compounds of this family: ammonia, carbon
dioxide and air.

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Ammonia (R-717)
o Ammonia is a colorless gas with a strong pungent odor which may
be detected at low levels (e.g., 0.05 ppm). Liquid ammonia boils at
atmospheric pressure at -33°C. The gas is lighter than air and very
soluble in water.

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Despite of its high thermal capability to provide cooling, it may
cause several technical and health problems includes:
o Gaseous ammonia is extremely irritating to eyes, throat, nasal
passages and skin (exposure to levels in the range of 5 to 30
ppm, reported to eye irritation.
o Exposure to levels of 2500 ppm causes permanent eye
damage, breathing difficulties, and asthmatic spasm and chest
pain.
o Non-fatal poisoning may lead to the
development of bronchitis, pneumonia, and
an impaired lung function.
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o Ammonia is a flammable gas and forms potentially explosive
mixtures with air in the range of 16% to 25% ammonia in air.
o Ammonia vapors react with the vapors of acid (e.g., HCl) to
produce an irritating white smoke.
o Ammonia and ammonia-contaminated oil must be disposed of in a
proper way approved by local regulatory agencies.
Note: Ammonia is an excellent refrigerant and
indicated that these possible disadvantages can be
eliminated with proper design and control of the
refrigeration system.
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Carbon dioxide (R-744)
It is oldest inorganic refrigerants, it is colorless, odorless, nontoxic,
non-flammable and non-explosive refrigerant and can be used in
cascade refrigeration systems, dry-ice production and food freezing
applications.

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Air (R-729)
✓ Air is generally used in aircraft air conditioning and refrigeration
systems.
✓ Its coefficient of performance is low because of the light weight
of the air system.
✓ In some refrigeration plants, it may be used in the quick freezing
of food products.

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4. Azeotropic mixtures
An azeotropic refrigerant mixture consists of two substances (cant be
separated by distillation) having different properties but behaving as a
single substance.
✓ The most common azeotropic refrigerant is R-502, which contains
48.8% R-22 and 51.2% R115.
✓ its lesser toxicity provides an opportunity to use
this refrigerant in household refrigeration
systems and the food refrigeration industry.

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5. Non-azeotropic mixture
✓ Non-azeotropic mixture is a fluid consisting of multiple
components of different volatiles that, when used in
refrigeration cycles, change composition during evaporation
(boiling) or condensation.
✓ Non-azeotropic mixtures became more attractive in research and
development on advanced vapor compression heat pump
systems.

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Non-azeotropic mixture offered the following advantages:
• Energy improvement and saving
• Capacity control
• Adaptation of hardware component regarding capacity and
applications limits.

Note:
Widely used refrigerants such as R-l 1, R-12, R-22,
and R-114 became most popular for the pure
components of the non-azeotropic mixtures.

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➢ Secondary Refrigerants
o Secondary refrigerants play a role in carrying heat from an object
or a space being cooled to the primary refrigerant or the
evaporator of a refrigeration system during this it has no phase
change.
o The most common secondary refrigerants were brines, which are
water-salt (e.g., sodium chloride and calcium chloride) solutions,
and even today they are still used in spite of their corrosive
effects.

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o The antifreezes, which are solutions of water and ethylene glycol,
propylene glycol, or calcium chloride, are widely used as
secondary refrigerants.
o Propylene glycol has the unique feature of being safe in contact
with food products.
o Dichloromethane (CH2Cl2), trichloroethylene (C2HCl3), alcohol
solutions, and acetone have also been used in some special
applications.

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The following features are considered as main criteria in the
selection of a proper secondary refrigerant;
o Satisfactory thermal and physical properties
o Stability
o Non-corrosiveness and non-toxicity
o Low cost and usability

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➢ Prefixes and decoding of refrigerants
o Various refrigerants (e.g., CFCs, HCs, HCFCs, HBFCs, HFCs, PFCs,
and halons) are numbered according to a system devised.
o Although it may seem confusing, in fact it provides very complex
information about molecular structure and also easily
distinguishes among various classes of chemicals.

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▪ Prefixes
o Most common refrigerant’s prefixes are CFCs, HCFCs, HFCs, PFCs,
and halons. In CFCs and HCFCs, the first 'C' is for chlorine (Cl), and
in all of them, 'F' is for fluorine (F), 'H' is for hydrogen (H) and the
final 'C' is for carbon (C).
o PFC is a special prefix meaning
'perfluorocarbon'. 'Per' means 'all', so
perfluorocarbons have all bonds occupied by
fluorine atoms.

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Prefixes and atoms in refrigerants
Name Prefix Atoms contained
Chlorofluorocarbon CFC Cl, F, C
Hydrochlorofluorocarbons HCFC H, Cl, F, C
Hydrobromofluorocarbon HBFC H, Br, F, C
Hydrofluorocarbon HFC H, F, C
Hydrocarbon HC H, C
Perfluorocarbon PFC F, C
Halon Halon Br, Cl, H, F, C

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▪ Decoding the number
It helps us to find out the number of each types of atom, and the key
to the code is to add 90 to the number; the result shows the number
of C, H and F atoms. e.g., For HCFC-141b:
141+90= 2(#C) 3(#H) 1(#H).

✓ All of these chemicals are saturated, so that

they contain only single bonds, the number of
bonds available in carbon based molecule is
2C+2. thus for HCFC-141b, which has 2 C
atoms, there are 6 bonds.

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Cl atoms occupy bonds remaining after the F and H atoms. So, HCFC-
141b has 2C, 3H, 1F and 2Cl.
HCFC-141b = C2H3FCl2

Note:
Where, the HCFC designation is a good double-
check on the decoding; containing H, Cl, F, and C.
The 'b' at the end describes, how these atoms are
arranged; different 'isomers' contain the same
atoms, but they are arranged differently.

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➢ Isomers
Isomers of a given compound contain the same atoms but they are
arranged differently and having different properties.
All of the compounds under discussion are based on carbon chains
(1-3 carbon atoms attached in a line of single bonds: e.g., C-C-C,
the naming system is based on how H, F, Cl, Br atoms are attached
to that chain.

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✓ A single C atom can only bond with four other atoms in one way,
so there are no isomers of those compounds.
✓ For two-C molecules, a single lowercase letter following the
number designates the isomer.
✓ For three-C molecules, a lower-case two-letter code serves this
purpose. e.g., Consider two-C molecules, e.g., HCFC-141, HCFC-
141a, and HCFC-141b in which all have the same atoms (2C, 3H,
1F, and 2Cl), but they are organized differently.

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✓ To determine the letter, total the atomic weights of the atoms
bonded to each of the carbon atoms. The arrangement that most
evenly distributes atomic weights has no letter.
✓ The next most even distribution is the 'a' isomer, the next is 'b',
etc. until no more isomers are possible.

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A common way of writing isomers' structure is to group atoms
according to the carbon atom with which they bond. Thus, the
isomers of HCFC-141 are:
✓ HCFC-141: CHFCl - CH2Cl (atomic weights on
the 2 C = 37.5 and 55.5)
✓ • HCFC-141 a: CHCl2 - CH2F (atomic weights on
the 2 C = 21 and 72)
✓ • HCFC-141b: CFCl2 - CH3 (atomic weights on
the 2 C = 3 and 90)

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Selection of Refrigerants
There are many criteria for the selection of the refrigerants for the
use in a refrigeration or heat pump systems. The refrigerants are
expected to meet the following conditions;
✓ Ozone and environment friendly,
✓ Low boiling temperature,
✓ Low volume of flow rate per unit capacity,
✓ Vaporization pressure lower than atmospheric
pressure,
✓ High heat of vaporization,

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Cont…
Selection of refrigerants
✓ Noncorrosive and nontoxic,
✓ Non-acidic in case of a mixture with water or
air,
✓ Chemically stable,
✓ Suitable thermal and physical properties
✓ Easily detectable in case of leakage, and low
cost.
✓ Non-flammable and nonexplosive,
✓ Non-corrosive and nontoxic,
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 Introduction to Refrigeration
Refrigeration
o Refrigeration is the process of removing heat from matter which
may be a solid, a liquid, or a gas. Removing heat from the matter
cools it, or lowers its temperature.
o The lowering of temperature in older methods, may be
accomplished by rapid expansion of gases under reduced pressure.
o Thus, cooling may be brought about by
compressing air, removing the excess heat
produced in compressing it, and then
permitting it to expand.
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A lowing of temperature is also produced by adding certain salts, such
as sodium nitrate, sodium thiosulfate and sodium sulfite to water.
There are two common methods of refrigeration; natural and
mechanical.
In natural refrigeration, ice has been used in refrigeration since
ancient times and still in used.
o In this process, forced circulation of air passes
around blocks of ice as a result some of the
heat of air is transferred to ice, thus cooling of
air particularly for air conditioning applications.

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 In mechanical refrigeration, a refrigerant is a substance capable of
transferring heat that it absorbs at low temperatures and pressures
to a condensing medium; in the region of transfer, the refrigerant is
at higher temperatures and pressures.
o By the means of expansion, compression and
cooling medium, such as air or water, the
refrigerant removes heat form a substance and
transfer it to the cooling medium.

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 Refrigeration System
Main refrigeration systems and cycles
o The main goal of a refrigeration system which performs the reverse
effect of a heat engine is to remove the heat from a low-level
temperature medium (heat source) and to transfer this heat to a
higher level temperature medium (heat sink).
o In these systems, the refrigerant is used to transfer the heat.
o The refrigerants absorbs heat (Temperature is
lower than source) hence increase in
temperature during the process to a temperature
higher than the heat sink’s temperature.

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 Refrigeration System and cycle
Heat sink
TH
▪ TL :The absolute temperature of source
▪ QL: heat transferred from the source is
QH
the refrigeration effect (refrigeration
W
System load)
refrigeration ▪ The heat rejection to the sink at the
Work
QL Input temperature TH is QH
Heat Source ▪ W: Work input
TL
Figure: Thermodynamic
system acting as a refrigerator

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 History of Refrigeration
o For centuries, people have know that the evaporation of water
produces a cooling effect. At least as early as the second century
evaporation was used in Egypt to chill jars of water, and it was
employed in ancient India to make ice.
o Depending on this phenomena, in 1755, a Scottish physician, William
Cullen, obtained sufficiently low temperatures for ice making.
o In 1834, Jacob Perkins, an American residing in
England, constructed and patented a vapor-
compression machine with a compressor, a
condenser, an evaporator.
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 History of Refrigeration
o New substances, e.g., ammonia and carbon dioxide, which were
more suitable than water and ether, were made available by
Faraday, Thilorier, and others, and they demonstrated that these
substances could be liquefied.
o The theoretical background required for
mechanical refrigeration was provided by
Rumford and Davy, who had explained the
nature of heat by Kelvin, Joule and Rankine,
and continuing work with Sadi Carnot in
formulation of science of thermodynamics in
1946.
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 History of Refrigeration

o Refrigeration machine was appeared between 1850 and 1880,

and classified according to refrigerants.
o Dr. John Gorrie, an American, developed a real commercial cold
air machine and patented in 1951.
o Refrigerating machines using cold air as a refrigerant were
divided into two types, closed cycle and open cycle.

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 History of Refrigeration
o In Europe. Dr. Alexander C. Kirk (1862) and Franz Windhausen
(1870) invented a closed cycle refrigeration machine and patented.
o The open cycle refrigeration machine was theoretically outlined by
Kelvin and Rankine in the early 1850s.
o It was invented by a Frenchman, Paul Giffard in 1837 and by Josep
J. Coleman and James Bell in Britain in 1877.

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 History of Refrigeration
o In 1860, a French engineer, Ferdinand P. Edmond Carre invented an
intermittent crude ammonia absorption apparatus based on the
chemical affinity of ammonia and water, which produced ice on
limited scale.
o A comparatively large-scale ice making absorption unit was
constructed in 1878 by F. Windhausen.
o It operated continuously by drawing water from
sulfuric acid with additional heat to increase
the affinity.

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 History of Refrigeration
o The vapor compression machine was invented and patented by an
American professor, Alexander C. Twining in 1853.
o He established an ice production plant using this system in
Cleveland, Ohio and could produce close to a ton per day.
o In France F.P.E. Carre developed and installed an ether-compression
machine and Charles Tellier construct a plant using methyl ether as
a refrigerant.

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 History of Refrigeration

o Linde had paved the way for great improvement in refrigeration

by demonstrating how its thermodynamic efficiency could be
calculated and increased.
o Inventors of compression machines also experimented with
ammonia, which became the most popular refrigerant and was
used widely for many years.

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 History of Refrigeration
o In the 1860s Tellier developed an ammonia-compression machine.
o The ammonia had thermodynamic advantage, the pressures it
required were easy to produce, and machines which used it could
be small in size.
o In the late 1860s, P.H. Van der Weyde of
Philadelphia got a patent for a compression
unit which featured a refrigerant composed of
petroleum product.

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 History of Refrigeration
o In 1875 R.P. Pictet at the University of Geneva introduced a
compression machine that used sulfuric acid.
o In 1866 T.S.C. Lowe, an American, developed refrigerating
equipment that used carbon dioxide.
o Between 1880 and 1890 ammonia-compression installations
became more common.
o By 1890 mechanical refrigeration had proved to
be both practical and economical for the food
refrigeration industry.

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 History of Refrigeration
o Steady technical progress in the field of mechanical refrigeration
marked after 1890.
o The revolutionary changes were not the rule, but many
improvements were made, in several countries, in the design and
construction of refrigerating units, as well as in their basic
components, compressor, condensers and evaporators.

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 References

➢ Ibrahim Dincer, Refrigeration systems and applications, John

Wiley & Sons, Ltd.,(2003), ISBN 0-471-62351-2.

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Thank You

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