Technology College Mechanical Engineering Department

Refrigeration and Air-conditioning

(MEng 4711)

Lecture 4
Refrigerants

Introduction
Any body or susbstance that acts as a cooling medium by

extracting heat from another body or substance. In a closed cycle systems, refrigerant is any working fluid that undergoes cyclic changes during system operation. A refrigerant is a substance that picks up latent heat when the substance evaporates from a liquid to a gas. This is done at a low temperature and pressure. A refrigerant expels latent heat when it condenses from a gas to a liquid at a high pressure and temperature. The refrigerant cools by absorbing heat in one place and discharging it in another area.

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Introduction
Properties of an ideal refrigerant A high latent heat of vaporization Non-toxic, non-flammable and non-corrosive Compatible with component materials Not mix with oil since compressors are lubricated.

Operate at moderate pressures to reduce compressor

work and leakage. Be relatively cheap to produce and store. Ease of leak detection Environmental friendly

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Classification of Refrigerants
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 vapor compression and vapour absorption refrigeration systems. When used in compression or absorption systems, these fluids provide refrigeration by undergoing a phase change process in the evaporator. Secondary refrigerants are those liquids which are used for transporting thermal energy from one location to another. Secondary refrigerants are also known under the name brines or antifreezes.
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Classification of Refrigerants
If the operating temperatures are above 0oC, then pure

water can also be used as secondary refrigerant, for example in large air conditioning systems. Antifreezes or brines are used when refrigeration is required at sub-zero temperatures. Unlike primary refrigerants, the secondary refrigerants do not undergo phase change as they transport energy from one location to another. 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.
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Classification of Refrigerants
The primary refrigerants are further classified into the following four

groups: Halo-carbon Refrigerants Azeotropic and Zeotropic Refrigerants Inorganic Refrigerants and Hydro-carbon Refrigerants Halo-carbon refrigerants: The American Society of Heating, Refrigeration and Air-conditioning Engineers (ASHRAE) identifies 42 halo-carbon compounds as refrigerants, but only a few of them are commonly used for e.g. R-12,R-22, R-114 etc. Azeotropic Refrigerants: The term 'azeotrope' refers to a stable mixture of refrigerants whose vapour and liquid phases retain identical compositions over a wide range of temperatures. However, these mixtures usually have properties that differ from either of their components. The example of Azeotrope Refrigerants are R-500 (73.8% R-12 & 26.2% R-152), R-502, R-152 etc.
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Azeotropic Refrigerants
A stable mixture of two or several refrigerants whose

vapour 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 R-503 : 40.1% R23 and 59.9% R13

Zeotropic Refrigerants
A zeotropic 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%)

Classification of Refrigerants
Inorganic Refrigerants: The inorganic refrigerants were

exclusively used before the introduction of halocarbon refrigerants. These refrigerants are still in use due to their inherent thermodynamic and physical properties; for example Ammonia R-717, Air R-729, CO2 R-744 etc. Hydro-carbon refrigerants: Most of the hydro-carbon refrigerants are successfully used in industrial and commercial installations. They possess satisfactory thermodynamic properties but are highly flammable and explosive e.g. Ethane R-170,Propane R-290,Propylene R1270 etc.

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CFC Refrigerants
The

first halogen-based refrigerants (fluorinated hydrocarbons) were developed over sixty years ago carbon, and are called chlorofluorocarbons (CFCs).

These refrigerants are composed of chlorine, fluorine, and

These refrigerants are low in toxicity, noncorrosive, and

compatible with other materials. They are not flammable or explosive with, but sizable quantities must not be released where there is a flame or electric heating element. They are particularly harmful to the respiratory system.
Common CFC refrigerants include R-11, R -12, R -113,R -

114,R -115, R-500, R-502, and R-503.

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CFC Refrigerants
R-500, R-502, and R-503 are azeotropic mixtures but are

classified as CFCS by the American Society of Heating, Refrigeration, and Air Conditioning Engineers (ASHRAE).
CFCs are thought to be one of the major causes of ozone

depletion. By international agreement, they have not been

manufactured since 1995. However, they are still widely used in existing residential units

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HCFC Refrigerants
Hydrochlorofluorocarbons

(HCFCS) are molecules composed of methane or ethane in combination with a halogen. This makes up a new molecule that is considered to be partially halogenated. The HCFCs have shorter lives and cause less ozone depletion than the fully halogenated CFCS. Therefore, they have reduced potential for global warming. HCFCS such as R-22 and R-123 are considered to be interim refrigerants. They will be used until suitable replacements are available. The EPA requires the phase out of HCFCs by the year 2030.
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HFC Refrigerants
Hydrofluorocarbons (HFCs) include such

refrigerants as R-134a and R-23. They are different from chlorofluorocarbons-they contain one or more hydrogen atoms and no chlorine atoms. HFCS are considered to have zero potential for ozone depletion. They have only a slight effect on global warming.

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Refrigerant Blends(Azeotropic- Zeotropic)

Another more recent category is that of refrigerant blends,

commonly referred to as "azeotopic" and "zeotropic." The use of refrigerant blends is increasing. Azeotropic blends do not change or separate in composition when used in Refrigeration systems. Zeotropic refrigerants are also blends composed of various refrigerants. when used in a refrigeration system, their volumetric composition and saturation temperature do not change.

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Refrigerant Selection Criteria

In order to select the a correct refrigerant, it is

necessary that it should satisfy those properties which make it ideal to be used for a particular application. The considered properties are: Thermodynamic properties, Chemical properties, Physical properties Environmental and safety properties/concerns & Cost

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Refrigerant development
Refrigerant development can be devided into three

phases:
1.

2.
3.

Early refrigerants (prior to CFCs) Chloro-fluoro-carbon (CFC) based refrigerants Refrigerants after Montreal protocol

1. Early Refrigerants Ethyl ether is the first refrigerant to be used by Jacob Perkins in 1835.

Ether is liquid at ambient conditions Ether boiling point is 34C0 at 1atm: for low temperatue conditions, the evaporator should work at vacuum. Possibility for leakage and explosive mix Ether is toxic
Alexander Twinning proposed the use of ammonia and CO2 in 1850.

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Ammonia is important refrigerant in todays applications It has good thermal properties, easily available, Thursday, March 14, 2013 inexpensive, easy to handle

Refrigerant development

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Charles Tellier used dimethyl ether as refrigerant in 1864. it is toxic Raoul Pictet used SO2 as refrigerant in 1874. It is not flammable: it is flame detergent. Acts as auto-lubricant! In the presence of water, it forms acid which is toxic and corrosive to the system. Linde builed a system based on NH3 as refrigerant in 1877. Imporant land mark in refrigerant development! Excellent thermodynmic and thermophysical property! But is toxic, strong smell and slightly flammable Windhausen used CO2 as refrigerant in 1885. Non toxic and non flamable thus safe! Imporant application in marine refrigeration and air conditioning. It needs high operating pressure.
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Refrigerant development
Problems with Early Refrigerants

Toxicity (eg. Ethers, Ammonia) Flammability (eg. Hydrocarbons) Material compatibility (eg. Ammonia) Chemical stability (eg. SO2) Operating Pressure (eg. CO2) Limited temperature range (eg. All)

Developments of refrigerants which are non-toxic, non-flamable, material compatible, chemically stable!!

Chloro-Flouro-Carbon (CFCs) refrigerants invented!!! 18

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Refrigerant development
Chloro-fluoro-carbon (CFC) based refrigerants

Thomas midgley and his associates take up the task of developing refrigerants that are free from problems associated with early refrigerants in 1928 in USA.

CFCs are synthesized by replacement hydrocarbons!!

Hydrocarbon

A series of refrigerant family are formed!!!

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Refrigerant development
Chloro-fluoro-carbon (CFC) based refrigerants

CFCs in the trade name of FREONS enter the market in 1930s!! Freon-12 (CCl2F2) is introduced in 1931 and widely used in domestic refrigeration!!! Freon-11 (CCl3F) is introduced in 1932 and widely used in air conditioning in large plants!!! Freon-22 (CHClF3) and other CFCs are developed!!! A numbering system is developed for identifying the different drived refrigerants!

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Refrigerant development
Early refrigerants vs. CFCs

Compared to the early refrigeratnts, CFCs have solved the previous problems!!! non-toxic Non-flammable Chemically stable Compatable with common materials
Avaialble for a wide refrigeration temperature

Becuase of the favorable properties, CFC refrigeratnts became popular and get extensive application!!
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Refrigerant development
IMPACT OF CFCs

All early refrigerants except ammonia are replaced by various CFCs! Rapid growth in refrigeration due to the widespread use of CFCs! Refrigeration enters Households in the form of domestic refrigerators and air conditioners, thanks to CFCs! Production and consumption of CFCs increased exponentially!!
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Refrigerant development
OTHER SIDE OF CFCs: Ozone layer depletion

In 1974, Rowland and Molina propose the theory of Ozone Layer Depletion due to CFCs released into atmosphere! Stratosphere and Ozone layer:

15-50Km

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Refrigerant development

Ozone layer depletion

Ozone is imporant to protect life on earth from UV radiation. UV is harmful to life on earth! Ozone layer depletion consequences For human beings, increased instances of : Skin cancer Weakened immune systems Damages DNA structure cataracts Adverse effect on crop yield Adverse effects on terrestrial and aquatic ecosystem

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Refrigerant development

Ozone layer depletion

In 1974, Rowland and Molina propose the theory of Ozone Layer Depletion due to CFCs released into atmosphere! Subsequent studies show Ozone depleting potential (ODPs) of CFCs and related substances!
o

R-11 (CFCl3) as a reference! =1ODP

o

o
o
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Example: R-12 = 1 ODP R-114 = 0.8 ODP R-22 = 0.055 ODP

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Refrigerant development

CFCs and Global Warming

CFCs act as greenhouse gases and hence contribute significantly to Global warming! Atmoshperic blanket keeps the earth warm and this is essential for life on earth! The atmoshperic blancket consists of several gases (greenhouse gases) such as CO2 N2, H2O!!

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Refrigerant development

CFCs and Global Warming Solar radiation mainly consists of long and short wave radiation. Atmoshperic blanket with greenhouse gases allows short wave radiation to pass and reach the earth, while absorbing the long wave radiations. The earth surface absorbs these shortwave radiations and keep warm! The earth also emmits long wave radiations and these are absorbed at the atmoshpere (by the greenhouse gases)!! absorb longwave radiation and transmit short wave radiations!! 27 Thursday, March The earth is kept warm!! Without GHG: T = -14, 2013

Refrigerant development

CFCs and Global Warming The temperature condition in the atmoshpere with out any additives is balanced for this situation! With the presence of large scale CFCs, the balance of global warming is disturbed! CFCs are capable of absorbing much more long wave radiations compared to the conventional greenhouse gases such as CO2!!

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Global temperature increase!!

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Refrigerant development

CFCs and Global Warming Global warming potential (GWP) of CFCs is determined with respect to CO2. CO2 as a reference! =1GWP CFCs = several thousands of GWP R11 = 3800 GWP R12 = 8100 GWP R114 = 9300 GWP R22 =1700 GWP

Montreal Protocol!!
Ban CFCs with ODP and GWP!
R11, R12, R113, R114, R502 phase out by year 2000 R22 phase out by year 2030!
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Refrigerant development
Refrigerants after Montreal protocol (3rd generation of refrigerants) Replacements for CFCs should be:

Non-ozone depleting Have as low GWP as possible

Several Synthetic and natural refrigerants are found to replace CFCs Some of the early refrigerants such as CO2 make a comeback! Application CFCs HFC 134a, HCs Domestic and Replacements CFC 12 CFCs refrigerators
Air conditioning
CFC 11, CFC 12, HCFC 22 HFC 134a, HCs, CO2, and mixtures

Cold storages
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HCFC 22, R 502

Ammonia, HFC mixtures

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Designation of refrigerants
Before the invention of chlorofluorocarbons (CFCs),

refrigerants were called by their chemical names. Because of the complexity of these names, especially the CFCs the fully halogenated CFCs, and hydrochlorofluorocarbons (HCFCs), the not fully halogenated HCFCs, a numbering system was developed for hydrocarbons and halocarbons and is used widely in the refrigeration industry. From the number one can get some useful information about the type of refrigerant, its chemical composition, molecular weight etc. The refrigerants are internationally designated as 'R' followed by certain numbers such as R-11, R-12, R-114 etc.
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Designation of refrigerants
A refrigerant followed by a two digit number indicates that

a refrigerant is derived from methane base while three digit number represents ethane base. The numbers assigned to hydro-carbon and halo-carbon refrigerants have a special meaning. The first digit on the right is the number of fluorine (F) atoms in the refrigerant, the second digit from the right is one more than the number of hydrogen (H) atoms present. The third digit from the right is one less than the number of carbon (C) atoms, but when this digit is zero, it is omitted.

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Designation of refrigerants
The general chemical formula for the refrigerant, either for

methane or ethane base, is given as CmHnClpFq, in which n+p+q = 2m+2 where m = Number of carbon atoms, n = Number of hydrogen atoms, p = Number of chlorine atoms, and q = Number of fluorine atoms. As discussed above the number of the refrigerant is given by R (m - 1)(n +1) (q) e.g., R12 = CCI2F2
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Designation of refrigerants
Inorganic refrigerants These are designated by number 7 followed by the molecular weight of the refrigerant (rounded-off). Examples: Ammonia: Molecular weight is 17, the designation is R 717 Carbon dioxide: Molecular weight is 44, the designation is R744 Water: Molecular weight is 18, the designation is R 718

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Designation of refrigerants
Mixtures Azeotropic mixtures are designated by 500 series, whereas zeotropic refrigerants (e.g. non-azeotropic mixtures) are designated by 400 series. Examples R500, R502, R503, R404A, R407A Hydrocarbons Propane (C3H8) : R290 n-butane (C4H10) : R600 iso-butane (C4H10) : R600a Unsaturated Hydrocarbons: R1150 (C2H4) R1270 (C3H6)
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Seminar Assignment
Major Equipment of Vapor-Compression Refrigeration

Systems: Group 1: Compressors Group 2: Condensers Group 3: Evaporators Group 4: Expansion Devices (Flow Control Devices) Assessment (10%)
Report (5%) Presentation (5%)

Report and presentation should include Types, Principle of

operation, Performance Analysis.

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Grouping
Group 1: (Ecaporator) Group 3: (Compressor)

Yoftahe 2. Redia 3. Tadesse

1. Group 2: (condeser)

Asehafi 2. Andualem 3. Chalachew

1. Group 4: (Exapansion

Acham 2. Dereje 3. G/Medhin

1.

Device) 1. Lijalem 2. Zinabu 3. Mengestab

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