Application Guide

AG 31-007

Refrigerants
Gas Refrigerant Out

Chilled Water In

Chilled Water Out

Water in Tubes TX Valve

Liquid Refrigerant In

Lower Toxicity Higher Flammability Lower Flammability No Flame Propagation

Higher Toxicity

A3 A2 A1

B3 B2 B1

2002 McQuay International

Contents
Introduction ............................................................................................................. 3 What Is A Refrigerant?............................................................................................ 4 Common Refrigerants ............................................................................................. 5 What Makes A Good Refrigerant?.......................................................................... 8 Refrigerant Chemistry ........................................................................................... 21 Refrigerants and Refrigeration Systems ................................................................ 24 Stratospheric Ozone Depletion.............................................................................. 28 Montreal Protocol and the EPA............................................................................. 30 Climate Change and Refrigerants.......................................................................... 39 Kyoto Protocol ...................................................................................................... 42 Refrigerants in The Future .................................................................................... 44 Conclusions ........................................................................................................... 48 References ............................................................................................................. 49 Appendix 1 R-134a MSDS Sheet ......................................................................... 51 Appendix 2 Refrigerant Properties....................................................................... 59 Appendix 3 Sample Pressure-Enthalpy Diagram .................................................. 64

The information contained within this document represents the opinions and suggestions of McQuay International. Equipment, the application of the equipment, and system suggestions are offered by McQuay International as suggestions only, and McQuay International does not assume responsibility for the performance of any system as a result of these suggestions. Final responsibility for system design and performance lies with the system engineer.

Application Guide AG 31-007

Introduction
In the mid nineteen-eighties the world recognized that CFC refrigerants, once considered safe for people as well as the planet, were in fact severely damaging the Earths ecology. Refrigerants suddenly went from being rarely discussed during the design of a building to becoming a major consideration for the consulting engineer. There was much confusion and speculation at that time, as refrigerants became a strong marketing point for HVAC equipment manufacturers. It was often difficult for decision-makers to get clear answers to their questions. Although the CFC issue is, for most part, behind us, significant issues concerning persist. The purpose of this guide is to provide detailed refrigerant background information to increase understanding of how refrigerants can affect our business and personal lives. While this guide was prepared by McQuay International, which clearly has a stake in refrigerant applications, there are many footnotes and an extensive bibliography drawing from many renowned, non-partisan sources.

Application Guide AG 31-007

What Is A Refrigerant?
At the end of the last millennium, there were many Top Ten lists made, including one listing the greatest invention of the twentieth century. Along with space flight and computers, refrigeration made the top ten because without refrigeration, food preservation would not be possible. In addition, there could not be high rise office buildings or modern health care facilities. Websters dictionary defines refrigerants as a substance used in a refrigerating cycle or directly such as ice for cooling. A person from outside the HVAC industry might describe a refrigerant as some kind of fluid used in an air conditioner. Many within the HVAC industry would immediately think of CFCs (Chlorofluorocarbons). All these definitions are accurate, but refrigerants are much more than that. Water is the refrigerant used in absorption chillers. Carbon Dioxide (CO2) and Ammonia (NH3) are known as natural refrigerants. Flammable substances such as propane and isobutane are also used as refrigerants. To this group, CFCs, HCFCs and HFCs can be added. ASHRAE Standard 34, Designation and Safety Classification of Refrigerants, lists over 100 refrigerants, although many of these are not used on a regular commercial HVAC basis. Refrigerants are chemical substances. Some substances known as refrigerants (e.g. R-141b) are used in diverse applications such as a foam blowing agent, which has little to do with cooling spaces.

Refrigerant History
Mechanical refrigeration has been around since the mid-nineteenth century. The first practical machine was built by Jacob Perkins in 18341. It was based on using ether as a refrigerant in a vapor compression circuit. Carbon Dioxide (CO2) was first used as a refrigerant in 1866 and Ammonia (NH3) in 1873. Other chemicals used as vapor compression refrigerants included chymgene (petrol ether and naphtha), sulfur dioxide (R-764) and methyl ether. Their applications were limited to industrial processes. Most food preservation was accomplished by using blocks of ice collected during the winter and stored or manufactured through an industrial process. By the beginning of the twentieth century, refrigeration systems were being used to provide air conditioning in major building projects. The Milam Building in San Antonio, Texas was the first high-rise office building to be completely air conditioned2. In 1926, Thomas Midgely developed the first CFC (Chlorofluorocarbons), R-12. CFCs were nonflammable, non-toxic (when compared to Sulfur Dioxide) and efficient. Commercial production began in 1931 and quickly found a home in refrigeration. Willis Carrier developed the first centrifugal chiller for commercial use and the era of refrigeration and air conditioning began. For technical reasons that will be discussed later, several refrigerants became very popular in air conditioning including CFC-11, CFC-12, CFC-113, CFC-114 and HCFC-22. While the fledgling air conditioning industry grew into a multi billion dollar industry, very little changed on the refrigerant front. By 1963, these refrigerants represented 98% of the organic fluorine industry. By the mid 1970s, concerns began to surface about the thinning of the ozone layer and whether CFCs may be in part responsible. This led to the ratification of the Montreal Protocol in 1987 that required the phase out of CFCs and HCFCs. New solutions were developed with HFCs taking on a major role as refrigerants. HCFCs continued to be used as interim solutions and at the time of writing this document were beginning to be phased out. In the 1990s global warming arose as the new threat to the well being of the planet. While there are many contributors to global warming, refrigerants were again included in the discussion because air conditioning and refrigeration are significant energy users (about 1/3 of the energy in the USA is consumed in the operation of buildings) and many refrigerants are themselves greenhouse gases.
1

Thevenot, R. 1979. A History of Refrigeration Throughout the World. International Institute of Refrigeration (IIR) 2 Pauken, M. May 1999. Sleeping Soundly on Summer Nights. ASHRAE Journal
4 Application Guide AG 31-007

Common Refrigerants
Although there are many substances classified as refrigerants by ASHRAE Standard 34, only a handful are used for commercial air conditioning. Following is quick a rundown of the common refrigerant groups that are either in use or have been used in the past. Table 1 provides technical data on common refrigerants.

Water, R-718
Most refrigeration processes use either an absorption cycle or a vapor compression cycle. Commercial absorption cycles typically use water as the refrigerant with a salt solution such as Lithium Bromide as the absorbent. Water is non toxic, non-flammable, abundant etc. It is a natural refrigerant. The challenge for absorption chillers is that even a double-effect absorption cycle only has a COP (Coefficient Of Performance) slightly greater than 1 (Centrifugal chillers have COPs greater than 5). From a life cycle analysis point of view, absorption chillers require a thorough investigation to determine whether they offer a financially viable solution. Software programs such as McQuays Energy Analyzer can be used for this analysis. From an environmental point of view, the use of water as a refrigerant generally, is very good. The low COP might indicate that larger amount of fossil fuels will be required to operate an absorption chiller over a centrifugal chiller. This is not guaranteed however, since absorption chillers use fossil fuels directly, while electric chillers operate on electricity, a secondary energy source. The choice of which to use will be affected by how the electricity is actually generated.

Ammonia, R-717
Ammonia (NH3) is a natural refrigerant and considered to be one of the most efficient. It is one of the only original refrigerants still in use today. It is used in vapor compression processes, typically with positive displacement compressors. ASHRAE Standard 34 classifies it as a B2 refrigerant (higher toxicity lower flammability). ASHRAE Standard 15 requires special safety considerations for Ammonia refrigeration plants. Ammonia is mostly used in industrial applications, although there are many large commercial air conditioning installations that utilize it as well.

Carbon Dioxide, R-744

Carbon dioxide (CO2) is a natural refrigerant. Its use was phased out at the turn of the century, but new research aimed at using it again is currently under way. It is used in vapor compression processes with positive displacement compressors. The required condensing pressure is over 900 psig at 90F, which is a challenge. Also, the critical point is very low and efficiency is poor. Still, there may be applications, such as cascade refrigeration, where CO2 will be useful.

Application Guide AG 31-007

Hydrocarbons
Propane (R-290) and isobutane (R-600a), among other hydrocarbons, can be used as refrigerants in the vapor compression process. In Northern Europe, about 35% of refrigerators are based on hydrocarbons. They can have low toxicity and good efficiency but they are highly flammable. The latter issue has severely limited their use in North America where current safety codes restrict their use.

Chlorofluorocarbons (CFCs)
There are many Chlorofluorocarbons (CFCs) but the most common ones for air conditioning are R-11, R12, R-113 and R-114. CFCs were in popular use up to the mid-eighties. Production of CFCs was phased out by the Montreal Protocol in developed countries in 1995. Theyre still being manufactured and used in developing countries (but are scheduled for phase out soon). They are used in vapor compression processes with all types of compressors. The common CFCs are stable, safe (by refrigerant standards), non-flammable and efficient. Unfortunately, they also have damaged the ozone layer.

Hydrochlorofluorocarbons (HCFCs)
Hydrochlorofluorocarbons (HCFCs) have been around almost as long as CFCs. HCFC-22 is the most widely used refrigerant in the world. HCFC-123 is the interim replacement for CFC-11. They are used in vapor compression processes will all types of compressors. HCFC-22 is efficient and classified as A1 (lower toxicity no flame propagation). HCFC123 is efficient and classified as B1 (higher toxicity no flame propagation). Like CFCs, these refrigerants are being phased out as required by the Montreal Protocol. Production has been capped and soon will be ratcheted down in developed countries. Developing countries also have a phase-out schedule but on an extended timeline.

Hydrofluorocarbons (HFCs)
Hydrofluorocarbons (HFCs) are relatively new refrigerants whose prominence arose with the phase out of CFCs. HFCs have no ozone depletion potential (ODP=0). HFC-134a is the replacement for CFC-12 and R-500. They are used in vapor compression processes with all types of compressors. The common HFCs are efficient and classified as A1 (lower toxicity no flame propagation).

Application Guide AG 31-007

Table 1 - Refrigerant Properties

General Information
Refrigerant a Number 11 12 22 32 123 125 134a 245fa 290 404a 407C 410A 500 507a 600 717 718 744 Chemical Name
a

Chemical a Formula CCl3F CCl2F2 CHClF2 CH2F2 CHCl2CF3 CHF2CF3 CF3CH2F CHF2 CH2 CF3 CH3CH2CH3

Molecular a Mass 137.4 120.9 86.5 52 153 120 102 134.05 44

Safety Group
a

Atmospheric b Lifetime (Yrs) 50 102 12.1 5.6 1.4 32.6 14.6 8.8 h <1

ODP

GWP 3800 8100 1500 650 90 2800 1300 820 ~0 h 3260 1530 1730 6010 ~0 0 <1 1

trichlorofluoromethane dichlorodifluoromethane chlorodifuoromethane difluoromethane 2,2-dichloro-1,1,1-trifluoroethane Pentafluoroethane 1,1,1,2-tetrafluoroethane 1,1,2,2,3-Pentafluoropropane Propane R-125/143a/134a (44/52/4) R-32/125/134a (23/25/52) R-32/125 (50/50) R-12/152a (73.8/26.2) R-125/143a (50/50) Butane Ammonia Water Carbon dioxide

CH3CH2CH2CH3 NH3 H2O CO2

58.1 17 18 44

A1 A1 A1 A2 B1 A1 A1 B1 A3 A1 A1 A1 A1 A1 A3 B2 A1 A1

1 1 .055 0 .02 0 0 0 0 0 0 .74

<1 N/A N/A N/A

0 0 0 0

Operational Information
Refrigerant a Number 11 12 22 32 123 125 134a 245fa 290 404a 407C 410A 500 507a 600 717 718 744 Normal Boiling Point a (F) 74.67 -21.55 -41.46 -60.97 82.08 -54.64 -14.93 58.82 -43.75 -51.66b -46.82b -60.83b -28.31 -52.79 31.04 -27.99 211.95 f -109 Velocity of e Sound (ft/s) @ 40 F 443 448 535 688 414 409 482 436.2 723 473 519 553 490 457 659 1319 1352 687 Critical Point Temp (F) 388.33 233.55 205.06 172.59 362.63 150.83 213.91 309.2 206.06 162.5 186.9 158.4 222.0 159.34 305.62 270.05 705.1 87.76
g

Press. (psi) 639.27 599.89 723.74 838.61 531.1 526.34 588.75 527.1 616.07 548.18 672.2 694.87 641.9 538.79 550.56 1643.71 3200.1 1069.99

Bubble (F) @ psi

Dew (F) @ psi

Glide (F)

Viscosity g Lbm/ft*h @ 40 F Liq. 1.304 .574 .503 .361 1.292 .457 .620 1.296 .291

Specific Heat at Btu/ibR @ 40F Liq. .2059 .2253 .2825 .3106 .2379 .3044 .2194 .3121 .6077 .3349 .3403 .3652 .2579 .3331 .5588 1.1094 1.0555 .6460

Thermal g Cond. Btu/h*ft*F @ 40F Liq. .0548 .0429 .0537 .0872 .0476 .0397 .0521 .0506 .0600 .0438 .0582 .0652 .0480 .0432 .0665 .3155 .3293 .0607

38.8 @ 100 37.0 @ 90 42.9 @ 140

39.8 @ 100 47.8 @ 90 43.2 @ 140

1.0 10.8 0.3

.405 .479 .380 .557 .401 .469 .392 3.738 .222

ASHRAE, 1997. ANSI/ASHRAE Standard 34-1997,Designation and Safety Classification of Refrigerants. Atlanta, Ga.: ASHRAE b 1995 IPCC Report: HFCs Table 2.9;CFCs and HCFCs Table 2.2(Houghton et al. 1996). c Ozone Secretariat UNEP (1996). h ARTI Refrigerant Database, based on WMO and IPCC assessments, August 1998. GWP shown are for 100 year integrated time horizon. e NIST Standard Reference Database 23, Version 6.01 (NIST 1996). g 2001 ASHRAE Fundamentals Handbook chapter 20. f Sublimes.
a

Application Guide AG 31-007

What Makes A Good Refrigerant?

General
At first glance properties such as lower toxicity, no flame propagation, efficiency, and cost effectiveness come to mind. Certainly these are important characteristics and ones that are well advertised. But selecting a refrigerant for use in a refrigeration or air conditioning process goes far beyond just these properties. For example, efficiency can mean many different things and can therefore cause misunderstanding and confusion. This section will delve into many aspects of what makes a good refrigerant. Most refrigerants are used in a vapor compression cycle. A basic understanding of that cycle will help one to better appreciate the complex issue of refrigerants.

The Vapor Compression Refrigeration Cycle

With the exception of absorption chillers, most commercial air conditioning systems are based on the vapor compression cycle. The process can be used to collect heat from air (an air conditioner) or from water (a chiller). It can reject the heat into air (air-cooled) or water (water-cooled). The process can even be applied as a heater by moving heat from cold fluid (outdoor air) to a warm fluid (indoor air). This is referred to as a heat pump. A water-cooled chiller will be used as an example. The chiller utilizes the vapor compression cycle to chill water and reject the heat collected from the chilled water plus the heat from the compressor to a second water loop cooled by a cooling tower. Figure 1 shows the basic refrigeration circuit. It consists of the following four main components: Figure 1-Basic Refrigeration Circuit
Cooling Water Discharge Line

Evaporator
The evaporator is a heat exchanger that removes the building heat from the chilled water, lowering the water temperature in the process. The heat is used to boil the refrigerant, changing it from a liquid to a gas.

Liquid Line Shutoff Valve

Condenser 3

Sight Glass

Hot Gas Control Valve

Compressor

Compressor
Suction Line Chilled Water Evaporator 1

Metering Device

The compressor assembly is made up of a prime mover (typically an electric motor) and a compressor. The compressor raises the pressure and temperature of the refrigerant gas.

Condenser
Like the evaporator, the condenser is a heat exchanger. In this case, it removes heat from the refrigerant causing it to condense from a gas to a liquid. The heat raises the water temperature. The condenser water then carries the heat to the cooling tower where the heat is rejected to the atmosphere.

Expansion Device
After the refrigerant condenses to a liquid, it passes through a pressure-reducing device. This can be as simple as an orifice plate or as complicated as an electronic modulating thermal expansion valve.
8 Application Guide AG 31-007

Pressure-Enthalpy Diagram
The Pressure-Enthalpy (P-H) diagram is another way of looking at the refrigeration cycle. It has the advantage of graphically showing the process, the cooling effect and the work required to make it happen. Figure 2-Refrigeration Circuit, P-H Diagram Figure 2 shows the Pressure-Enthalpy (PH) diagram for the same refrigeration circuit shown in Figure 1. The process for each of the components is indicated. The evaporator process is from point 1 to point 2. As the refrigerant changes from a liquid to gas, the pressure (and temperature) stays constant. The heat is being absorbed as a phase change (latent energy). The refrigeration effect is the change in enthalpy from 1 to 2, simply expressed as Btu/lb. of refrigerant circulated.

Pressure

1 Refrigeration Work

2 Compressor Work

The line from 2 to 3 represents the compression process. The work is the change in enthalpy from point 2 to point 3 times the flow of refrigerant. Simply, Btu/lb. times the lb./min equals compressor power. Compressors end up with the work of compression as heat in the refrigerant. The vertical aspect of the curve shows the rise in refrigerant pressure (and temperature) from 2 to 3.
Enthalpy

The next process takes place in the condenser. The first section (outside the refrigerant dome) is the desuperheating process. Once the refrigerant is saturated, condensation occurs and the refrigerant changes from a gas to a liquid. Like the evaporator, the line is horizontal indicating constant pressure (or temperature). The final process is the expansion device. This appears as a vertical line from point 4 to point 1, indicating the pressure (and temperature) drop that occurs as the refrigerant passes through the Thermal Expansion (TX) valve. Figure 3-Heat Exchanger Performance
118.3 psig R-134a

97F

HEAT OF CONDENSATION
1

2
T2 95F

ID FLU SER EN ND CO
LIFT (F)

E ATUR PER TEM

85F T1

Figure 3 shows the heat transfer process for both the condenser and the evaporator. Using the ARI design conditions, typical temperatures are shown. Looking at the condenser, the refrigerant temperature remains constant at 97F. The refrigerant is changing from a gas to a liquid and is releasing its latent heat of condensation. At the same time the tower water enters the condenser at 85F and is gaining sensible heat as its temperature rises to approximately 95F. The evaporator behaves similarly. In this case, the evaporator refrigerant temperature remains constant at 42F. The refrigerant is changing from a liquid to a gas while absorbing its latent heat of vaporization. The chilled water entering the evaporator at 54F is releasing sensible heat and its temperature is dropping to 44F.

1 54F T

CO

OL

ER

FL U ID T

EMP

ERAT

1 HEAT OF VAPORIZATION

UR E
T2 44F

36.6 psig R 134a

42F

SATURATED SUCTION TEMPERATURE {TR}

Application Guide AG 31-007

The pressure in either the evaporator or condenser will be the saturation pressure for the given temperature. These can be found on temperature-pressure charts. For HFC-134a, the condenser pressure at 97F is 118.3 psig. The evaporator pressure at 42F is 36.6 psig.

Refrigerant Properties
Following is a list of key properties of refrigerants that are considered in the design of a refrigeration system. The positive and negative nature of these properties is shown with examples.

Toxicity
Toxicity and flammability are the two key parameters used by ASHRAE to indicate the safety level of a refrigerant. ASHRAE Standard 34 has adopted a matrix as shown in Figure 4 that indicates the relative levels of these two parameters. Figure 4-STD 34 Refrigerant Safety Classification Lower Toxicity Higher Flammability Lower Flammability No Flame Propagation Higher Toxicity Toxicity of a substance is a relative matter. Almost anything can be toxic in some dosage. It not so much an issue of whether something is bad for you, as at what concentration it will do bodily harm. Reactivity (the opposite of stability) will be discussed in a moment as it pertains to atmospheric concerns. In terms of toxicity, often more reactive substances have increased toxicity. The undesirable balance is to have a substance that is stable enough to enter the body but then reactive enough to cause harm. Atmospheric stability (an issue for the environment) is not necessarily tied to this process. ASHRAE Standard 34 classifies refrigerants into either class A or class B. Figure 4 includes the definitions for Class A and B. Acute Toxicity Acute toxicity refers to short term, often high concentration level exposure to a substance. For instance, being in a mechanical room when a refrigeration circuit breaks and releases large amounts of refrigerant into the space.

A3 A2 A1

B3 B2 B1

Class A signifies refrigerants for which toxicity has not been identified at concentrations less than or equal to 400 ppm by volume, based on date used to determine Threshold Limit Value Time Weighted Average (TLVTWA) or consistent indices. Class B signifies refrigerants for which there is evidence of toxicity at concentrations below 400 ppm by volume, based on date used to determine Threshold Limit Value Time Weighted Average (TLV-TWA) or consistent indices. Class 1 indicates refrigerants that do not show flame propagation when tested in air at 14.7 psia and 70F. Class 2 signifies refrigerants having a lower flammability limit (LFL) of more than 0.00625 lb/ft at 14.7 psia and 70F and the heat of combustion (HOC) less than 8174 Btu/Lb. Class 3 refrigerants are highly flammable. They have a lower flammability limit (LFL) of less than 0.00625 lb/ft at 14.7 psia or 70F or the heat of combustion greater than or equal to 8174 Btu/Lb.

Chronic Toxicity Chronic toxicity refers to long-term repeated exposure to a substance. For instance, the kind of exposure a service technician might experience over a lifetime of working on refrigeration equipment. These values tend to be time weighted since a technician is not likely to spend repeated full days exposed to refrigerants. Acute toxicity levels are always higher than the chronic toxicity levels for a given substance. For this reason, most safety levels are based on chronic (conservative) toxicity levels, although the overall goal is to reduce both acute and chronic exposure risks.

10

Application Guide AG 31-007

Threshold Limit Value (TLV) The TLV is the airborne concentration of a substance and represents conditions under which it is believed that nearly all workers may be repeatedly exposed day after day without adverse health effects. In simple terms it is the maximum allowable concentration that will avoid chronic toxicity problems. The values are based on the best available information from industrial experience and experimental testing. There is a wide variation in individual susceptibility to substances so some people may experience discomfort at levels below the TLV. A pre-existing condition in an individual may cause a more aggravated response to exposure. Smoking may also aggravate an individuals response. Individuals may also be hyper-susceptible to some substances due to genetic factors, age, personal habit (smoking, alcohol or other drugs) medication or previous exposure. In these cases, the TLV may not provide an adequate indicator and an occupational physician should be consulted to determine whether any additional protection may be desireable.3 PAFT PAFT is the Program for Alternative Fluorocarbon Toxicity Testing. It is a co-operative effort sponsored by refrigerant manufacturers to accelerate the testing of fluorocarbon based (HFC) substances. These tests involve more than 100 tests, which can take up to six years and cost in excess of $5 Safety Consideration million. Consider two refrigerants in common use today, Ammonia (R-717) and R-22. PAFT tests cover acute toxicity, chronic toxicity, Standard 34 lists Ammonia as a B2 carcinogicity (cancer causing), genotoxicity (effects on refrigerant and R-22 as an A1 genetic material), teratology (effects on the refrigerant.. reproductive system and birth defects), ecotoxicity (effects on living organisms in the environment) among others4. Research from PAFT is used to help set the safety classifications and toxicity levels for many refrigerants recently introduced to the market place including R123, R-134a, R-141b, R-124, R-125 and R-32. R-32, R-125 and R-134a are used to produce R-410A and R407C. A quick review would indicate that Ammonia has higher toxicity than R-22, which is certainly true. However, R-22 is both a gas and heavier than air at atmospheric conditions. It is also odorless. It has killed because an unsuspecting occupant entered an enclosed low-lying space where the air had been displaced by R-22 leaked from a refrigeration system. Ammonia on the other hand has a strong odor, which can provide early warning to occupants. Any refrigerant can be used safely with proper procedures and any refrigerant can do harm if used improperly.

Other Safety Considerations Many refrigerants are used under considerable pressure (the average home air conditioner is operating at over 250 psig) which, if released in an uncontrolled manner, can be a threat. Possible splashing of liquid refrigerant, particularly into the eyes, is another concern. The low temperatures can cause frostbite if exposed to a leak. The flammability of a refrigerant also poses a potential threat. What is Safe? There is no clear-cut winner. Refrigerants have proven to be lethal in ways other than poisoning occupants. Many refrigerants are gaseous at atmospheric pressure and heavier than air. This means that the refrigerant will displace air in low-lying areas such as a basement mechanical room. An unsuspecting person entering such a space will suffocate rather than be poisoned. MSDS (Material Safety Data Sheets) offer an excellent source of information on the properties of a refrigerant. Appendix 1 R-134a MSDS Sheet shows a typical MSDS document.
3

1990-91 Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices. American Conference of Governmental Industrial Hygienists, Cincinnati, Ohio, 1990 4 PAFT 1993.PAFT Toxicology Summaries. Bristol, United Kingdom: Program For Alternative Fluorocarbon Toxicity Testing.
Application Guide AG 31-007 11

Flammability
Flammability is another key parameter in evaluating the safety level of a refrigerant. It is the second parameter that ASHRAE uses in Standard 34 when classifying refrigerant safety. Like toxicity, flammability is not as simple to evaluate as it may first appear. Most would consider water (R-718) to be non-flammable while Propane (R-290) is flammable. However, there are many substances that will burn given the right circumstances. What is required to make a substance combust also varies. Paper can be made to burn at room temperature by exposing it to open flame in standard air. Paper will also spontaneously combust at 451F without the presence of open flame. Standard 34 classifies refrigerants into three flammability classes.
!

Class 1 indicates refrigerants that do not show flame propagation when tested in air at 14.7 psia and 70F. Class 2 signifies refrigerants having a lower flammability limit (LFL) of more than 0.00625 lb/ft at 14.7 psia and 70F and the heat of combustion (HOC) less than 8174 Btu/Lb. Class 3 refrigerants are highly flammable. They have a lower flammability limit (LFL) of less than 0.00625 lb/ft at 14.7 psia or 70F and the heat of combustion greater than or equal to 8174 Btu/Lb.5

Lower Flammability Limit (LFL) The LFL of a refrigerant is the minimum homogeneous concentration in air that will propagate a flame. It is typically given as a percentage by volume. The test is based at 77F and 14.7 psia. To convert from a volume percentage to a density multiply the percentage by 0.0000257*(molecular mass) to obtain lb/ft. The actual test method is described in Concentration Limits of Flammability of Chemicals, ANSI/ASTM Standard E681-85, American Society of Testing and Materials, Philadelphia, Pa., 1984. Heat Of Combustion (HOC) The HOC is the heat released when a refrigerant is combusted in air and is expressed in Btu/lb. The number is positive when heat is released (exothermic) and negative when heat is required (endothermic). Flammability and Blends Blends create some interesting situations with regards to flammability. First, ASHRAE Standard 34 requires that each component of a blend already be a classified refrigerant. It is possible to have a Class 1 refrigerant blend, which has a class 2 substance as one of its constituents. For example, R-32 is classified as an A2 refrigerant and is used in both R-407C and R-410A, both of which are classified as A1 refrigerants.

Flammability Consideration Consider a refrigerator using propane (R-290) as a refrigerant. The refrigerator has a charge of approximately 0.5 lb in a kitchen that is 8 ft x 8 ft x 8 ft high. Propane is a gas at atmospheric pressure but is heavier than air. If a leak forms, the propane will diffuse throughout the space as a gas but will have heavier concentrations near the floor. The LFL for propane is 2.1%. To reach a flammable concentration in this example, 1.2 lb of propane would have to be released, which is more than twice what is in the refrigerator. However, the concentration will be higher near the floor, quite possibly high enough to cause an explosion if ignited. The point here is that flammability is not clear cut. Even with a flammable refrigerant such as propane, a hazardous situation is not certain.

Refrigerant developers will test for the critical flammability ratio, which is the maximum amount of flammable component that a mixture can contain and still be non-flammable regardless of the amount of air. As long as the refrigerant has a low enough critical flammability ratio, it will be class 1 refrigerant.

ASHRAE, 1997. ANSI/ASHRAE Standard 34-1997,Designation and Safety Classification of Refrigerants. Atlanta, Ga.: ASHRAE
Application Guide AG 31-007

12

Humidity, pressure and temperature will affect the flammability of a refrigerant. The flammability testing carried out for Standard 34 is based at 14.7 psia and 70F. It is possible to have refrigerants become flammable at higher temperatures and pressures.

Efficiency
Of all the properties of refrigerants, efficiency is the most misunderstood and most abused. To most people efficiency means how much energy do I have to provide to get a fixed amount of cooling? Useful refrigerating effect COP= Net energy supplied from external sources The more efficient the system, the less energy required to do the same amount of cooling. The issue is that efficiency is a system property not a refrigerant property! Many parameters control how efficient a refrigeration system is, many of which have little to do with refrigerants. The list includes motor efficiency, compressor efficiency (both at full and part load), heat exchanger design and materials, operating conditions etc. The refrigerant can affect the system efficiency in many ways including transfer properties (how easy is it to pump), heat transfer properties, acoustic velocity and so on. Carnot Cycle Figure 5 - Carnot Cycle

Efficiency Consideration Efficiency is a difficult parameter to comprehend. Carnot efficiency is the ultimate, but doesnt even take into account the refrigerant. Ideal cycles allow comparisons but again, these cycles cannot be obtained in the real world. Modeling real world efficiencies means taking into account heat transfer and transport properties and refrigeration system design. Refer to System Example page 29 for an indepth discussion on system efficiency.

TO

3
COMP WORK

ABSOLUTE TEMPERATURE, T

TR

COOLING EFFECT

ENTROPY S

The Carnot cycle is a theoretical cycle that is completely reversible. Figure 5 shows the Carnot cycle. The efficiency based on the Carnot cycle is; COP = TR /(TO - TR) Notice refrigerant is not part of the equation. It is possible to build refrigerant models and calculate the theoretical performance, but that requires making engineering decisions on the design of the system, the efficiency of the components etc so that any apples to apples comparison of refrigerants is not applicable. Different refrigerants will achieve optimal performance with different refrigeration system design. Using any one system design for analysis is unlikely to show competing refrigerants at their best performance.

Application Guide AG 31-007

13

Heat Transfer Properties

The main purpose of refrigeration is to move heat from where it is not wanted to where it is wanted (or at least not a problem). Heat transfer is key to this process. It is possible for a refrigerant to have run of the mill theoretical efficiency yet be an excellent performer because of its strong heat transfer performance. Good heat transfer allows close approaches in the heat exchangers. This in turn means smaller lifts for the compressor and improved efficiency. Many factors affect heat transfer. Several have to do with the refrigeration system itself such as piping design and material and flow rates (Reynolds numbers). Three key properties of the refrigerant also affect the overall heat transfer capability of the system. These are viscosity (), specific heat (cp) and thermal conductivity (k). The factors are used to calculate Prandtl numbers (Pr= cp/k) which are used in the design of the heat exchangers. The goal is to work with substances that can carry a lot of energy (high specific heats) and can transfer the energy easily (high thermal conductivity). It is also desirable to have low viscosity to enhance turbulence and reduce the work required to move the fluid.

Heat Transfer Consideration There is considerable marketing indicating that R-123 is the most efficient refrigerant. This is based on theoretical refrigerant models that do not take into account the heat transfer properties of the refrigerant. The models assume the energy will transfer at the design conditions specified. In fact, R-134a has better heat transfer properties than R-123.(see Table 1 Refrigerant Properties) This can lead to closer approaches in the heat exchangers and different refrigerant operating conditions (lower lift) for the same overall refrigeration system effect. The lower lift will reduce the power required and improve the system performance. ODP Consideration R-22 is an HCFC with a 0.055 ODP. Its production in developed countries has already been capped and its use in new equipment will be stopped in 2010 in the United States. Currently, R-22 is the most popular refrigerant in use and there is no clear drop in replacement for it. The ODP for R-22 is causing the entire industry to redevelop a significant portion of their product lines. GWP Consideration R-134a is an HFC refrigerant. HFCs are one of six chemicals in a basket that are specifically signaled out by the Kyoto Protocol on global warming as a greenhouse gas. While this means countries attempting to meet the requirements of the Kyoto Protocol must be careful how they use HFCs, it does not mean there is a phaseout. There is no reason for HFCs not to be considered a viable solution as a refrigerant now or in the future. A better measure of the warming impact of refrigerants is TEWI (See TEWI, Page 40).

Ozone Depletion Potential (ODP)

ODP is an index of a substances ability to destroy atmospheric ozone6. Table 1 lists the ODP for many common refrigerants. Note that R-11 and R-12 have the highest potential (1.0). While the ODP of a refrigerant does not affect its performance as a refrigerant, it is a key parameter. All refrigerants with any ODP either have been or will be phased out as required by the Montreal Protocol. Any new refrigerant/product development must be based on refrigerants with no ODP.

Global Warming Potential (GWP)

GWP is an index of a substances ability to be a greenhouse gas. This is covered in detail in the chapter on Climate Change. The GWP is relative to the warming effect of a similar mass of carbon dioxide for a 100 year time-frame. Carbon dioxide is used as the reference gas because it has the greatest net impact on global warming. Halocarbon refrigerants typically have higher GWPs than carbon dioxide but are in much smaller quantities.

Wuebbles, D.J. 1981. The Relative efficiency of a number of halocarbons for destroying Stratospheric ozone. Report UCID-18924, Livermore, Ca; Lawrence Livermore National Laboratory (LLNL)
Application Guide AG 31-007

14

The GWP of a refrigerant does not in itself exclude it from use but should be considered when evaluating it. Of greater importance is TEWI (total equivalent warming impact) which is covered in a later section.

Materials Compatibility
How a refrigerant reacts to other material used in a refrigeration circuit is critical to its real world application. Refrigerants will come into contact with copper, steel, brass, lubricants, gaskets, motor wind insulation, etc. All these must be checked carefully for compatibility. Foreign substances, such as moisture, must also be considered as part of a real world review. One of the great benefits of CFCs was how stable and inert they were. This made materials compatibility straightforward. Unfortunately, it is the inherent stability of CFCs that led to their downfall since they have a very long atmospheric lifetime. As more environmentally friendly refrigerants are used, the materials challenge often increases. Motor Windings Many compressors use hermetic motors where the motor is exposed to the refrigerant for cooling it. Refrigerants and insulation can interact through the refrigerant extracting polymers from the insulation or the insulation absorbing the refrigerant. When polymers are extracted, the insulation can Materials Compatibility become brittle, delaminate and otherwise degrade. Consideration These can lead to a motor failure. The extracted In most cases extreme care is taken polymers can deposit elsewhere in the refrigeration during the design of a refrigeration system and cause sticking and blockage. system that material compatibility issues Where refrigerants are absorbed by the insulation, are resolved beforehand. In the case of the dielectric strength or physical integrity can be a retrofit to a new refrigerant, the onus degraded. Rapid release of absorbed refrigerant on compatibility shifts to the field when the windings heat up can cause blistering and technician. When the market place first premature failure of the windings. started moving away from CFC refrigerants to HCFC-123 and HFCThe magnetic wire insulation is typically heat cured 134a, there was considerable emphasis enamel. The enamel insulating performance is placed on materials compatibility reduced when exposed to refrigerant at elevated because HCFC-123 in particular was temperatures as opposed to air. not compatible with insulation and Special care is taken when selecting motor insulation gasket materials used in R-11 chillers. based on the refrigerant chosen. Of special interest is Once materials compatible with either when the refrigerant specification is changed. It is R-11 or R-123 were identified, chillers critical that the materials used in the original design were often supplied with the new be compatible with the new refrigerant. materials regardless of the refrigerant used. This resolved a major cost in Elastomers and Plastics retrofitting these chillers in the field. Gaskets, O-rings, etc. can be made from elastomers. Today, almost half of the CFC based Refrigerants, lubricants or a combination of both can chillers are still in use. Many will be extract enough filler to adversely change the replaced at the end of their useful life. properties of elastomers. This can lead to shrinkage Those that are considered for or swelling which will cause the gasket to fail. Some retrofitting will need a full evaluation. neoprenes tend to shrink in HFC refrigerants while 7 Chillers that were not upgraded to nitriles tend to swell in R-123 . Plastics can also be materials compatible with HCFC-123 affected by refrigerants. The effect of refrigerants on will cost significantly more to upgrade. plastics usually decreases as the amount of fluorine in the refrigerant molecule increases.

Haned, G.R. and R.H. Seiple. 1993. Compatibility of refrigerants and lubricants with elastomers. Final Report No. DOE/CE 23810-14. ARTI Database. Air-conditioning and refrigeration Technology Institute, Arlington, Va.
15

Application Guide AG 31-007

Refrigerants and Metals Halocarbon refrigerants generally are very stable when exposed to metals. Under extreme conditions such as extreme heat, refrigerants can react with metals.8 ANSI/ASHRAE Standard 97 provides a method for accelerated life materials compatibility testing by raising the temperature. In tests conducted by Imagination Resources Inc. R-12, R-500, R-123 and R-134a were exposed to copper, steel, aluminum and Sunisco 4GS oil following the Standard 97 procedure. Only R-123 showed signs of materials incompatibility.

Lubricants
Just like an automobile engine, the mechanical components of a refrigeration system must be lubricated. These include the compressor and various valves (including the TX valve) throughout the system. The goal of a good lubricant is to protect moving parts, improve sealing in the compressor (viscosity), be chemically compatible with the refrigerant and the other materials within the refrigeration system, have a low solubility in refrigerant and be safe. In DX (Direct Expansion See Glide in Evaporators, Page 18) refrigeration circuits, the lubricant often travels with the refrigerant throughout the circuit, lubricating components along the way. Care must be taken in the design of the piping to make sure the oil will return to the compressor and not be trapped somewhere in the circuit. In flooded refrigeration systems, it is very easy for the lubricant to become trapped in the evaporator so it does not return to the compressor and also lowers the heat transfer effectiveness of the evaporator. In flooded systems, it is normal to have a lubricant return system that separates the lubricant from the refrigerant (an oil separator for instance) and return it to the compressor. Since it is expected that the lubricant and the refrigerant will mix, they must be compatible. Materials used for lubricants include mineral oils, alkyl benzenes, polyol esters (POE), poly-alkene glycols, modified polyalkylene glycols and polyvinyl ethers. The two most familiar to commercial air conditioning are mineral oils and polyol esters or POE lubricants. Mineral oils are natural (derived from crude oil). POE oils are synthetic and manufactured from alcohols. Refrigerants and Lubricants How refrigerants interact with lubricants is critical to the proper operation of the refrigeration system and its longevity. CFC refrigerants often used mineral oils for lubricants. The Chlorine in the refrigerants provided good anti-wear characteristics, so little or no additives were required. Mineral and POE oils are not compatible. Although mixing these oils should not happen in normal circumstances, it may happen if the refrigerant is changed within the system. HCFC refrigerants may use either mineral or synthetic lubricants. In some cases additives are used to improve lubricant performance. HFC refrigerants typically require a synthetic lubricant such as POE type.

Lubricant Consideration Consider changing a negative pressure R-11 chiller to R-123. The original CFC refrigerant used a mineral oil. This oil has circulated throughout the refrigeration circuit and has come into contact with nearly every inner surface. Now the new HCFC-123 requires a synthetic lubricant such as a POE. While the POE lubricant and R-123 are compatible, the POE and mineral oil are not. The challenge now becomes, how do you remove all the previous mineral oil prior to adding the new POE lubricant? This challenge had to be overcome before R-123 could be considered a viable replacement for R11. The problem was overcome by developing proper procedures for changeouts and adding additives to the POE lubricant to improve its compatibility with trace amounts of mineral oils.

Eiseman, B.J. 1963. Reactions of chlorofluoro-hydrocarbons with metals ASHRAE Journal 5(5):63
Application Guide AG 31-007

16

POE and Water POE oils are more hygroscopic than mineral oils. That is, they absorb moisture very easily. Moisture within a refrigeration circuit is detrimental because the moisture can mix with carbon to form carbonic acid. Special care must be exercised by operators and technicians not to expose the POE lubricants to atmosphere where they will absorb moisture. This moisture can be introduced to the refrigeration circuit if the lubricant is then added.

Critical Point
Figure 6 - Critical Point
Critical Point

Liquid

Mixture

Gas

Critical point is the point on a PressureEnthalpy (P-H) diagram where the properties of liquid and vapor refrigerant meet and become indistinguishable. The temperature, density and composition of the substance are the same for a liquid or gas at this point. The properties at the critical point are referred to as the critical density, critical pressure, critical volume and critical temperature. When operating at conditions above the critical point no separate liquid phase will be possible. Refrigeration cycles requiring condensation (most standard air conditioning cycles) will not be possible. It is possible to reject heat at super critical temperatures which is where current

P (pressure)

h (Enthalpy)

research into carbon dioxide is concentrating. Operating below but near the critical point typically offers high volumetric capacity but low efficiency since the refrigeration effect is reduced9.

Glide
Glide is a relatively new term to the market place that has surfaced with the advent of zeotropic refrigerant blends such as R-407C and R-410A. Zeotropic blends are comprised of refrigerant components that dont behave as one substance. Glide is the difference (in F) between the beginning and end phase change process of a refrigerant in either the evaporator or the condenser. It does not include subcooling or superheating. For example R-407C is made up of R-32 (-62F boiling point), R-125 (-56F boiling point) and R-134a (-15F boiling point). When R-407C is boiled (the evaporation process) R-32 will boil first, the remaining substance will have a different composition and hence a different average boiling point. This change in composition is known as fractionation. This changing of the average boiling temperature is the glide.

Critical Point Consideration Consider R-410A, a front runner to replace R-22 in many applications. It has a critical point of 158.4F as compared to R-22s critical temperature of 204.8F. Where this is an issue is in air-cooled products in high ambient locations such as the U.S. south west. Here the design ambient condition is often 105F or higher. Add to this a 25F refrigerant approach and now R410A is only 28F from its critical point. R-410A is being pushed to the top of its dome leaving very little room for condensation. The result is reduced efficiency. It is not unusual for a 5 ton R-410A condensing unit at ARI conditions to be reduced to only a 3 ton condensing unit in high ambient areas.

McLinden, M.O., and D. A. Didion. 1987. Quest for alternatives. ASHRAE Journal 29, Atlanta Ga.

Application Guide AG 31-007

17

Figure 7 - Zeotropic Behavior (R-134a/32) Figure 7 shows a zeotropic mixture of R-134a and R-32 where the ratio of R-32 is varied from 0 to 100%. By drawing a line vertically through the graph, the difference between the temperature as a liquid (lower line) and the temperature as a vapor (top line) can clearly be seen. The difference between the two lines is the glide.

55 45 35

T vap T liq

Te mp era tur e, F

P= 64 PSIA
25 15 5 -5 0 20 40 60 80 100

% R-32

Glide in Evaporators There are two main types of evaporators used in the air conditioning industry, DX (Direct Expansion) and flooded. DX evaporators have the refrigerant in the tubes and either water (chillers) or air (DX coil) on the outside. Flooded evaporators are used in chillers and they have the water in the tubes and the refrigerant in the shell. Figure 8 - DX Evaporator DX evaporators are more forgiving to refrigerants with glide than flooded evaporators are but as a system component, they are less efficient. Figure 8 shows a DX evaporator. In this design, the refrigerant passes through the thermal expansion device (TX valve) and is atomized into very fine liquid droplets in the tubes of the evaporator. The fine droplets offer a large amount of surface area to absorb

TX Valve Liquid Refrigerant In Gas Refrigerant Out

Refrigerant in Tubes

Chilled Water In

Chilled Water Out

heat from either air or chilled water on the outside of the tubes. Zeotropic refrigerants with glide will fractionate in the tubes. The compounds with lower boiling points will boil first followed by the other compounds. The high amount of superheat used in DX evaporators will make sure all the refrigerant subcomponents are boiled (converted to a gas) and the relative mass ratios will be maintained. Figure 9 - Flooded Evaporator
Gas Refrigerant Out

Chilled Water In

Chilled Water Out

Water in Tubes TX Valve

Liquid Refrigerant In

Figure 9 shows a flooded evaporator. The liquid refrigerant fills the shell and covers all the tubes. The heat from the chilled water in the tubes boils the refrigerant, which floats to the top of the shell. The inlet of the compressor draws in the gaseous refrigerant. The process is very similar to water boiling in a pot on a stove.

18

Application Guide AG 31-007

The issue with zeotropic refrigerants that have significant glides is that as the refrigerant fractionates, the compound with the lowest boiling point floats to the top first and enters the compressor. The relative mass ratios are not maintained. Zeotropic Serviceability Since zeotropic refrigerants fractionate, there is an issue when there is a leak. The problem for the technician is, which subcomponent leaked? It cannot be assumed that the subcomponents leaked in their design ratio. One solution would be to remove the entire charge and reload the refrigeration circuit with new refrigerant where the subcomponent ratio was known to be correct. This, however is not always practical. Glide Consideration Consider two of the frontrunners to replace R-22, R-407C and R-410A. Both are zeotropes. However, the glide for R-407C is 8F while the glide for R410A is only 1F. The high glide for R407C means it can be practically used only in DX systems, which limits the overall system efficiency that can be expected when using it. R-410A can be used in flooded systems, so even though it requires complete redesign of all components including the compressors (it operates at a significantly higher pressure), it is the common choice for redesigned refrigeration systems.

For small leaks, adding new refrigerant has been shown to have minimal impact on the system performance. In an experimental study10, a refrigeration system charged with R-407C had 12.5% of its charge removed (the ratio of subcomponents was not maintained) and then was recharged with brand new R-407C (proper subcomponent ratio). The process was repeated four times so half the initial charge was replaced. Table 2 shows the initial and final concentrations of the subcomponents before and after the leak/recharge process. Table 3 shows the performance loss with the leak/recharging. Dupont provides similar results (9% loss) based on theoretical models11. Table 2 - Initial and Final Concentrations at Different Locations
HFC-32/HFC-125/HFC-134a Location Initial Reciever Inlet Reciever Outlet Evaporator Inlet Evaporator Outlet Condenser Inlet Condenser Outlet 23.2/25.5/51.3 22.9/25.3/51.8 29.7/30.8/39.5 22.1/24.9/53.0 25.0/26.6/48.4 24.2/26.1/49.7 Weight % After 4 leak/recharges 20.1/22.6/57.3 20.0/22.6/57.4 26.8/28.4/44.8 19.9/22.5/57.6 21.6/23.6/54.9 21.4/23.5/55.0

Table 3 - Reduction in Performance After Leak/Recharge

Parameter Refrigeration Capacity Electrical COP Volumetric Capacity Reduction, % calculated with R-407C Concentrations 2.7 1.0 3.0 Reduction, % calculated with Real Concentrations 11.0 3.9 8.0

Charging zeotropic blends is more involved because only liquid can be added. The heal or last bit of refrigerant in the tank cannot be used. Special tanks that allow only liquid to enter are required.

10

Paulas-Lanckriet, M., O. Buyle .July, 1998. Experimental Study on Fractionation of R-407C and Recharge Operations. International refrigeration Conference at Purdue. 11 Retrofit Guidelines for Suva 407C, ART-34. June 2000. Dupont. Wilmington, De.
Application Guide AG 31-007 19

Acoustic Velocity
Acoustic velocity is important to refrigeration system design because it sets the speed limit on refrigerant flow. Approaching supersonic speeds can lead to shock waves that will damage equipment. It is not unusual for the refrigerant gas velocity entering the inlet of a centrifugal compressor to be near supersonic (Mach=1.0). Acoustic velocity increases when temperature increases, and decreases when pressure increases. Table 1 shows the acoustic velocity for common refrigerants. The conditions are given in the footnotes. Acoustic Velocity Consideration In the mid-nineties, CFC refrigerants were phased out. Companies that had the technology to build R-12 based chillers quickly converted to R-134a. In a general sense, R-134a was considered a drop in replacement for R-12 or R500. However the acoustic velocity in R-134a is about 8% higher than in R12. To truly optimize the machinery for R-134a, refrigerant pathways had to be modified and in particular, the inlet geometry of the impeller reduced and improved.

Physical Properties
There are several key physical properties of refrigerant that are an indicator of their potential. In particular, atmospheric boiling point and freezing point. The boiling point is a direct indicator of the temperature level the refrigerant can be used at. The freezing point must be lower than any contemplated operating point. Physical Properties Consideration Boiling point can be used to show the difference between R-123 and R-134a, the two common refrigerants for centrifugal chillers. R-123 boils at 82.17F at 14.7 psia. To lower the boiling point to approximately 40F so that the refrigerant goes from a liquid to a gas (the evaporation process), the refrigerant must be placed in a vacuum. Hence the negative pressure chiller concept. R-134a boils at 15.08F at 14.7 psia. To raise the boiling point to 40F, the refrigerant must be placed under pressure. Reviewing water (R-718) can show an example of the importance of freezing point. Water is used as the refrigerant in absorption chillers and it freezes at 32F at 14.7 psia. It is not possible to use a water-lithium bromide absorption chiller to chiller brine to below freezing. Absorption chillers will not be used in ice storage systems!

20

Application Guide AG 31-007

Refrigerant Chemistry
General
It is really quite remarkable that with the nearly infinite number of substances in the universe, only a handful are suitable for refrigerants. Many efforts have been made to source other families of compounds that perform as well as the group (Fluorocarbons) Thomas Midgley Jr. found in 1928. None so far have proven to be comparable. The following section provides a brief explanation of the chemical properties of the refrigerants in use today. It will provide the foundation for discussion of the challenges facing chemists in developing new refrigerants.

Inorganic Compounds
Water (R-718), carbon dioxide (CO2) (R-744) and ammonia (NH3) (R-717) are examples of natural refrigerants. Many were used in early development of refrigeration systems with water (absorption chillers) and ammonia being the only two in wide commercial use today.

Fluorocarbons
Most of the modern refrigerants (CFCs, HCFCs and HFCs) are derived from fluorocarbons. The results of varying the ratios of fluorine, carbon and hydrogen can be shown in Figure 10. Figure 10 Trade-offs in Varying F, Cl and H in Refrigerants Adding chlorine or bromine (moving to the HYDROGEN lower left corner of the triangle) increases the ODP of the substance. Adding chlorine Flammable also tends to raise the boiling point13. Adding fluorine to the substance (moving to the lower right corner of the triangle) tends to increase the GWP of the substance. The GWP depends on infrared absorbence (carbon-fluorine bonds) and longevity. Increasing the fluorine also tends to reduce toxicity.14
Long Atmospheric Lifetime (fully halogenated)

12

Toxic

Increasing the hydrogen content (moving up the triangle) tends to increase flammability. It also tends to decrease its atmospheric lifetime, which is a positive feature in light of global warming. CFCs, which have no hydrogen, have the longest lifetimes and are not flammable. Hydrocarbons (propane, isobutane) are highly flammable but have short atmospheric lifetimes.

CHLORINE

FLUORINE

12

McLinden, M.O., and D. A. Didion. 1987. Quest for alternatives. ASHRAE Journal 29, Atlanta Ga. 13 McLinden, M.O., and D. A. Didion. 1987. Quest for alternatives. ASHRAE Journal 29, Atlanta Ga. 14 Clayton, Jr., J.W. 1967. Fluorocarbon toxicity and the biological action. Fluorine Chemistry Reviews.
Application Guide AG 31-007 21

Blends
Blends are mixtures consisting of two or more compounds. With only a finite number of refrigerants available, new refrigerants made up of two or more other refrigerants increases the possibilities. By careful formulation it is possible to create a new refrigerant that will take advantage of existing technology (e.g. R-407C) or optimize new technology (e.g. scroll compressors and R-410A).

Azeotropes
Azeotropic refrigerants are blends made up of two or more refrigerants that have the same equilibrium vapor and liquid phase compositions at a given pressure. More simply stated, the refrigerant blend behaves as one refrigerant throughout the refrigeration cycle and does not fractionate. The slope of temperature vs. composition line is zero (no glide). Examples include R-500 and R-502. ASHRAE Std 34 designates Azeotropes with 500 series numbers. Figure 11 - Azeotropic Refrigerants
AZEOTROPIC BEHAVIOR (R-125/R-143a)
39 T vap 38 T liq

Temperature, F

37 P=100 PSIA 36

35 R-507 = AZEOTROPIC MIXTURE R-125/R-143a (50/50) 34

33

10

20

30

40

50

60

70

80

90

100

% R-125

Zeotropes
Zeotropic refrigerants are blends that change volumetric composition and saturation temperature (glide) as they boil. In short, they will fractionate. ASHRAE Standard 34 designates Zeotropes with 400 series numbers. Examples include R-407C and R-410A. Both are considered frontrunners to replace R-22. For more information on Glide, see page 17.

Hydrocarbons
Hydrocarbons are compounds containing only hydrogen and carbon. Hydrocarbon refrigerant examples include R-290 (propane) and R-600a (isobutane). The term hydrocarbon is often misapplied to cover any flammable refrigerant. Hydrocarbons used as refrigerants are highly flammable but can be good refrigerants. They can cause cardiac sensitization but generally breakdown quickly enough so that they offer lower overall toxicity risks. Hydrocarbons have also been connected to smog formation15 because they are linked to ozone generation in the troposphere.

15

Corr, S., J.D. Morrison, F.T. Murphy and R.L. Powell, 1995. Developing the hydrofluorocarbon range: Fluids for centrifugal chillers. Proceedings of the 19th International Congress of Refrigeration, IIR. Paris, France
Application Guide AG 31-007

22

Chemical Trends
The following is a summary of trends16 that occur with the use of various elements:
! !

Increasing carbon generally increases the molecular weight and the boiling point. Increasing nitrogen generally makes the compound more reactive. This can lead to toxicity and instability issues. Increasing oxygen generally reduces atmospheric stability, which is good for GWP and ODP but may lead to toxicity, flammability and reactivity issues. Increasing sulfur generally increases toxicity and decreases stability. Increasing hydrogen generally reduces atmospheric lifetime, which is good for GWP and ODP but increases flammability. Increasing fluorine attached to carbon increases GWP. Increasing chlorine improves lubricant miscibility but also ODP and toxicity. Increasing bromine increases ODP but lowers flammability. Using boron in lieu of carbon creates chemicals that are reactive and generally toxic. Using silicon in lieu of carbon creates substances that adversely react with water and have not performed well thermodynamically.

! !

! ! ! ! !

Calm, J., David D. Didion, Oct 6-7, 1997. Tradeoffs in Refrigerant Selections: Past, Present and Future. Refrigerants for the 21st Century, ASHRAE/NIST Refrigeration Conference. ASHRAE, Atlanta, Ga.
Application Guide AG 31-007 23

16

Refrigerants and Refrigeration Systems

Refrigerants have many properties, which can affect their performance. These properties also affect which kind of refrigeration system they are used in and specifically what kind of compressor. Most commercial refrigeration systems are based on absorption or vapor compression technology. Absorption chillers use water as the refrigerant and lithium bromide as the absorbent. Other substances can be used as well, such as water and ammonia. Using water as the refrigerant limits the chilled water temperature (must stay above freezing) to conditions that are acceptable to commercial air conditioning.

Compressors
Vapor compression refrigeration systems utilize a compressor to raise the enthalpy (pressure and temperature) of the refrigerant which is often referred to as lift. The operating conditions dictate the required lift (see Figure 3-Heat Exchanger Performance). Air-cooled equipment will need a higher lift than water-cooled because of the warmer condensing temperatures. Low temperature applications will also require a higher lift. The amount of refrigerant effect (the tons of refrigeration) is proportional to the refrigerant flow rate (lb/min or cfm per ton). Positive displacement compressors tend to be high-lift, low-volume compressors. Examples include reciprocating, scroll and screw compressors. Centrifugal compressors tend to be low-lift, high flow rate compressors. Figure 12 Volumetric Capacity of Common Refrigerants

VOLUMETRIC CAPACITY
200 113 114

MOLECULAR MASS

150 124 125 502 507 143a 410A 32 12 134 22 152a 134a 500 11

123

100

50

0 .1 1 10 100

CFM/TON

Refrigerants with small molecular mass tend to lend themselves to high enthalpy, low flow rate applications. In other words, they match up well with positive displacement compressors. Examples include R-22, R-410A and R-134a. Using R-410A as an example, Figure 12 shows its small molecular mass. Figure 13 shows R-410A provides high delta enthalpy capability. Both figures show how R-410A only requires about 1.5 cfm/ton capacity making it a good candidate for positive displacement compressors. Refrigerants with large molecular size require high volume flow rates and tend to provide a smaller delta enthalpy. Examples include R-11 and R-123. Figure 13 shows these two refrigerants as strong candidates for centrifugal compressors. Both of these refrigerants require approximately 17 cfm/ton refrigerant flow.

24

Application Guide AG 31-007

R-134a is often used in both positive displacement and centrifugal compressors. Although it can be used with any kind of positive displacement compressor, it is often used with screw compressors because they have relatively high flow rates for a positive displacement type. R-134a requires a flowrate of approximately 3 cfm/ton. Figure 13 - Delta H Vs. CFM/Ton

WATER COOLED CHILLER DUTY

18 16

32 152a

POSITIVE DISPLACEMENT, ROTARY, SCROLL, RECIP, SCREW

14

DELTA H, (Btu/lb)

12 10 8 6 4

410A 22 143a 507 502 125 500 12 134 134a 124 114 11 123 113

CENTRIFUGAL
2 0 .1 1 10 100

CFM/TON

Heat Exchangers
Both the evaporator and the condenser are heat exchangers. A refrigerants ability to transfer energy to and from a heat exchanger will affect the overall system performance. Heat transfer is proportional to surface area and temperature difference among other things. If a refrigerant has poor heat transfer properties, either the surface area must be increased (adding copper tubing adds a lot of cost) or the temperature difference must be increased. Increasing the temperature difference means increasing the compressor lift which will increase the compressor work. In commercial air conditioning, temperature differences for chillers can be down to 1 or 2 degrees F so small changes are very important. As an example, R-123 has a thermal conductivity of 0.0476 Btu/hftF while R-134a has a thermal conductivity of 0.0521 Btu/hftF. The improved energy transfer provides the refrigeration system designer the choice of either reducing the copper tubing in the heat exchanger and thus lowering the cost or lowering the lift on the compressor and thus improving the performance.

Piping and Pressure Drops

All refrigerants, whether in vapor or liquid form, undergo a pressure drop as they flow through the refrigeration circuit. This can be in the piping connecting components or in a component (i.e. a compressor passageway). As the pressure changes, the temperature of the refrigerant changes as well. How much depends on the refrigerant. Changes in temperature generally adversely affect system performance. Consider pressure drops in the suction and discharge lines. So that there is the correct pressure (and temperature) at the evaporator and the condenser, the pressure drops (and hence temperature changes) will have to be added to the total lift the compressor provides. Which refrigerant is used affects the temperature change relative to the pressure change.

Application Guide AG 31-007

25

System Example
From an efficiency point of view, what is really important is to provide a system that meets the load (has enough refrigeration effect) for the least operating cost. In most cases, least operating cost means the least amount of energy input. Many refrigerant properties and the parameters discussed above all come together to affect the (energy) cost to operate the system. Following is an example of how all these properties interrelate. NIST Cycle_D, Version 2.0, a software program, was used to model the system performance.

Model Parameters
!

Compare R-134a to R-123. Because these two refrigerants are used in large chillers, there has been a significant amount of marketing on this subject. Design conditions will be based on ARI 550/590-98 chiller design conditions. Namely:
! !

44F supply chilled water temperature, 2.4 USgpm per ton 85F supply condenser water temperature, 3.0 USgpm per ton

Model 1 Carnot
The first model is based on Carnot cycle. This is the best possible refrigerant effect and will set a benchmark. This is independent of refrigerant and is based solely on the temperatures. The efficiency is 0.323 kW/ton. Table 4 - Refrigerant System Models
Model Property Chilled water Supply Temp (F) Cond. Water Supply Temp (F) Compressor Inlet Temp (F) Compressor Outlet Temp (F) Suction Line Press. Drop (F) Liq. Line Press. Drop (F) Evaporator Superheat (F) Condenser Subcooling (F) Isentropic Compressor Eff. Compressor Motor Eff. COP KW/ton Carnot Ideal Cycle R-123 44 85 44 95 0 0 0 0 100% 100% 8.949 0.393 R-134a 44 85 44 95 0 0 0 0 100% 100% 8.472 0.415 Base Model R-123 44 85 41 97 1 1 0 9.5 84% 100% 6.444 0.546 R-134a 44 85 42 96 1 1 0 9.5 85% 100% 6.506 0.541 Base Model w/ Non condensables R-123 44 85 41 99 1 1 0 9.5 84% 100% 6.201 0.567 R-134a 44 85 42 96 1 1 0 9.5 85% 100% 6.506 0.541

44 85 44 95 N/a N/a N/a N/a N/a N/a 10.88 0.323

Model 2 Ideal Cycle

The definition of an ideal cycle is not formalized. In this example it means isentropic compression (100% efficient), perfect heat transfer and no pressure drops (temperature changes) as refrigerant flows through piping and components. Notice the refrigerant temperatures are the same as the water temperatures (no approaches) which cannot be obtained in practice. As well, there are no losses for transport (suction or liquid line pressure drops). R-123 has the better performance. This is the basis for claims that R-123 is the most efficient refrigerant available. However, it is impossible to build a refrigerant system based on an ideal cycle.

Model 2 Base Model

The base model starts to allow for some real world performance. Notice there are approaches on the evaporator and the condenser (the refrigerant is a different temperature than the water). The approaches for R-123 are higher than for R-134a because R-134a has better heat transfer characteristics. The compressor efficiency is slightly lower (1%) for R-123 than for R-134a. The argument here is the transport properties for R-123 are worse than for R-134a adding losses to the compressor efficiency. Accounting for heat transfer and transport properties makes R-134a slightly more efficient.

26

Application Guide AG 31-007

Model 2 Base Model Allowing For Non-condensables

Finally, non-condensables in the negative pressure system have been added which raised the condensing pressure 2 F. This further worsened the performance of the negative pressure chiller and also showed the sensitivity efficiency has when non-condensables are added.

Summary
As soon as real world examples were modeled, choices had to be made about the system design. In fairness to R-123, the design favored R-134a. Subcooling significantly helps R-134a. Multistage compressors help R-123. If the Base Model conditions are repeated with R-123 and a multistage compressor the performance becomes 0.491 kW/ton (COP = 7.16). Accounting for noncondensables decreases the multi-stage performance to 0.508 kW/ton (COP = 6.92). By the same token, talking about ideal cycle efficiency and not accounting for heat transfer and transportation properties is not realistic either. The customer should really stay focused on the overall equipment performance and consider whether full load or partload performance should be optimized.

Application Guide AG 31-007

27

Stratospheric Ozone Depletion

The Earth is surrounded by a layer of Ozone in the Stratosphere that protects life from the Suns ultraviolet radiation (UV-B). Increased levels of UV-B at the Earths surface may lead to skin cancer and other adverse health effects. Plants, aquatic and other terrestrial life can also be affected. In 1970, Crutzen supposed that nitrogen oxides from fertilizers and supersonic aircraft might deplete the ozone layer. In 1974 Mario Molina and F. Sherwood Rowland identified CFC refrigerants as a source of chlorine in the stratosphere and the potential threat they proposed with increased use17. Both public and private research was started to investigate these theories. The ozone layer over the Antarctic was observed to be thinning in the austral spring for several seasons and the results were published in 198518. This became known as the ozone hole. The ozone hole has been observed every season since, varying in size and duration but generally increasing.

The Chemical Process

In the end, one of the key advantages of CFCs and HCFCs, their stability, became their Achilles heel. CFCs and HCFCs are stable molecules, they do not react easily with other substances which gives them a long atmospheric life. The long life allows the CFCs and HCFCs to rise high up into the stratosphere where the ultraviolet light decomposes the CFCs and HCFCs and frees the chlorine. Ozone on the other hand is very reactive. Once exposed to the free chlorine, it quickly breaks down in a catalytic process. The process releases the chlorine to react with another ozone molecule. A single chlorine atom can destroy thousands of ozone molecules. The effect is the thinning of the ozone layer. Other chemicals also contribute to ozone depletion including Halons, carbon tetrachloride, methyl chloroform, hydrobromofluorocarbons (HBFCs) and methyl bromide. Figure 14 - Atmospheric CFC Concentrations
1000 900 800 700 600 500 400 300 200 100 0 1975

total CFCs

ppt

R-12 all uses total CFC refrigerants R-12 refrigerant 1980 1985 Year 1990 1995 2000

The source for CFCs and HCFCs is not all refrigerant manufacture or emissions. Figure 14 shows concentrations of total CFCs, CFC-12 in all uses, total CFC refrigerants and R-12. Currently, about 27% of the CFCs in the atmosphere are from refrigerant emissions19. The balance of CFC emissions comes from

solvents, foam blowing agents, aerosols, etc. HCFC refrigerant emissions account for 83% of the total HCFCs found in the atmosphere. As of 1996, refrigerants were responsible for 28% of the anthropogenic (manmade) ozone depletion. Refrigerants over the next century will be responsible for 24% of the anthropogenic ozone depletion Refrigerants have been and will continue to be a major factor in ozone depletion.

17

Molina, M., F.S. Rowland. 1974. Stratospheric sink for chlorofluoromethanes: Chlorine-atom catalyzed destruction of ozone. Nature 249 18 Farman, J., B. Gardiner, J. Shanklin. 1985. Large losses of total ozone in Antarctica revealed seasonal C1O x NO x interaction. Science 190 19 AFEAS (Alternative Fluorocarbons Environmental Acceptability Study. 1997. Production, sales and atmospheric release of fluorocarbons through 1995. SPA-AFEAS Inc., Washington D.C.
28 Application Guide AG 31-007

Why Antarctica?
Actually some thinning of the ozone layer over the North Pole has been observed. The ozone occurrence has been linked over Antarctica to the presence of chlorine and bromine and unique Antarctic stratospheric weather, chemistry and physics. Antarctica has very cold polar stratospheric clouds (PSCs) which contain water and nitric acid crystals. When the sun hits (PSCs) in the austral spring the water and nitric acid crystals form reaction sites for the breakdown of ozone.

The Montreal Protocol

In 1987 the Montreal Protocol on Substances That Deplete the Ozone Layer (UNEP 1987) was ratified. It will be discussed in detail in the next section but the result was the phaseout of CFCs, HCFCs and several other ozone depleting substances.

Ozone Depletion in the Future

The concentrations of CFCs, HCFCs and other ozone depleting substances in the lower atmosphere peaked in 1994 and are now slowly declining. Recent evidence suggests that concentrations in the stratosphere may also have peaked.20 The ozone layer is expected to return to pre-industrial levels by the middle of this century. Figure 15 - Ozone Depletion Capacity (In equiv. Cl) Based On Global Adherence To 21 The Montreal Protocol

3500 3000 2500 ppt 2000 1500 1000 500 0 2000 2020 solvents

Total CFCs All Refrigerants HCFCs halons

2040 YEAR

2060

2080

2100

Schrope, M. Dec. 7, 2000.Successes in the fight to save ozone layer could close hole by 2050. Nature V408. 21 Frasier, P. 1998. Refrigerants: contributions to climate change and ozone depletion. AIRAH Journal, June 1998
Application Guide AG 31-007 29

20

Montreal Protocol and the EPA

Background
By the mid 1980s there was overwhelming evidence that the ozone layer needed to protect life on Earth was thinning and that this was due to manmade chemicals reacting with the ozone in the stratosphere. In 1985 the United Nations Environmental Program (UNEP) and the World Meteorological Organization (WMO) coordinated the Vienna convention which provided the framework for the Montreal Protocol. In 1987, the Montreal Protocol on Substances That Deplete the Ozone Layer (UNEP 1987) was ratified. This was a landmark event in that the majority of countries came together to identify a problem and agree on a solution.

Timeline
The original protocol has been amended several times over the years, adding substances, changing dates and so on. As well, the protocol differentiates between Annex 1 (developed countries) and Annex 2 (developing countries) providing different timelines for each group. The following is a summary on the original requirements and subsequent changes made over the years. The UNEP meets annually to discuss any further changes that the protocol may require so future changes are still possible.

Annex 1 (Developed) Countries22

DATE 1987 1990 1992 DETAILS Montreal Protocol: Requires 50% reduction in CFC production by 2000. Other compounds were also controlled. London Amendment: Requires 100% phaseout of CFC production by 2000. Copenhagen Amendment: Advances CFC phaseout to 1996. Set HCFC consumption cap in 1996 with a ratcheted phaseout as follows
! ! ! !

65% of Cap in 2004 35% of Cap in 2010 10% of Cap in 2015 And 0.5% of Cap in 2020

The cap was set as the ozone depletion potential weighted consumption for HCFC plus 3.1% of the CFC ODP weighted consumption wit ha base year of 1989. 1995 1997 1999 The CFC portion of the HCFC cap was reduced from 3.1% to 2.8%. Montreal Protocol Amendments: HCFC consumption from 2020 to 2030 only be used for service on existing equipment Beijing Amendments: HCFC production caps introduce to deal with export issues to developing countries.

22

Ozone Depleting Substances: Position Paper. Approved by the Board Of Governors, Feb. 1, 2001. ASHRAE, Atlanta Ga.

30

Application Guide AG 31-007

Annex 2 (Developing) Countries

DATE July 1999 2016 DETAILS Cap CFC consumption at the 1995-97 average levels and phase out consumption by 2010. Freeze HCFC consumption at 2015 levels phase out consumption by 2040.

EPA and CFCs

Production of CFCs stopped December 31, 1995, in the United States as required by the Montreal Protocol for developed countries. The only source of CFCs (in particular R-11 and R-12) is reclamation from existing equipment.

Montreal Protocol and HCFCs

The Montreal Protocol does not differentiate between HCFCs although it does require the cap be based on an ODP-weighted average. The phase out schedule for HCFCs as required by the Montreal Protocol is shown in Figure 16. Figure 16 - HCFC Phaseout as Per Montreal Protocol Many countries, including the United States, have modified versions of the Montreal Protocol phase out schedule, either choosing to accelerate the phase out of higher ODP substances or to exceed the minimum requirements set out in the protocol.

Montreal Protocol Cap 120 Montreal 65% - 2004 100 Protocol Cap 35% - 2010 80 10% - 2015 60 No Production 0.5% -2020 40 2030 20 0 1990 1995 2000 2005 2010 2015 2020 2025 2030 Year % or Cap Set by Montreal Protocol

The multi-tiered approach has led to much confusion regarding which dates are actually correct. For a country to be in compliance with the Montreal Protocol, they must meet the minimum requirements shown in Figure 16. If a country chooses to exceed the requirements, then whatever schedule was approved by the governing body will be the minimum requirement.

EPA and HCFCs

120 100 80 60 40 20 0
1990 1995 2000 2005 2010 2015 2020 2025 2030

HCFC-141b No Production

YEAR

The Environmental Protection Agency (EPA) is the governing body in the United States that ratified the Montreal Protocol into law. In July 1992, the EPA implemented section 604 of the Clean Air Act, which was in response to the Montreal Protocol. The cap for HCFCs went into effect in 1996 based on the 1989 baseline. For the United States, the HCFC cap is 15,240 ODP weighted metric

Application Guide AG 31-007

% of Original Cap Set by Montreal Protocol

31

tons. What is very important to understand is the phase out schedules required by the EPA and the Montreal Protocol are different. This has led to significant confusion in the market place, as several substances (R-22 for example) appear to have different phaseout schedules depending on which document is referenced. Figure 17 - EPA Cap on R-141b The EPA identified HCFCs that had higher ODPs and scheduled their phase-out sooner than other HCFCs with lower ODPs. In this manner the EPA intends to meet the ODP-weighted HCFC phaseout schedule required by the Montreal Protocol. So, although the EPA schedules are different from the Montreal Protocols schedule, they meet the same goal. The EPA has accelerated phase-out schedules for R-141b, R-142b and R-22. Figure 17 shows the phaseout schedule for R-141b, which is predominately used as a foam blowing agent. No production or importing is allowed beyond 2003. Phasing out R-141b will help the United States meet the 35% reduction in the HCFC cap required by the Montreal Protocol that goes into effect in 2004. Figure 18 EPA Cap on R-22 and R-142b Figure 18 shows the phaseout schedule for R-22 and R-142b. Again, this is faster than required by the Montreal Protocol but will allow the United States to meet the second major reduction in HCFC consumption required in 2010.

% of Original Cap Set by Montreal Protocol

120 100 80 60 40 20 0 1990 1995 2000 2005 2010 2015 2020 2025 2030 YEAR 0.5 % of Original Cap No Production HCFC 142b & 22

Of significant interest to the HVAC market is the phase out of R-22 in 2010. Only 0.5% consumption for service will be allowed beyond that date and only for another 10 years. R-22 is the most popular refrigerant in the world. Phasing it out affects nearly every kind of refrigeration system including home air conditioning, rooftop units, and industrial refrigeration. See Refrigerants in The Future for possible replacements to R-22. Figure 19 EPA Cap On Remaining HCFC Refrigerants Including R-123 Figure 19 shows the phaseout schedule for remaining HCFC refrigerants in use in Remaining HCFCs 120 the United States. The United States phase-out for 100 0.5 % of Original Cap remaining HCFCs for non80 refrigeration applications is 60 2015. Of key interest to the No Production 40 HVAC industry is R-123, 20 the interim solution for negative pressure 0 1990 1995 2000 2005 2010 2015 2020 2025 2030 centrifugal chillers.
% of Cap Set by Origional Montreal Protocol

The EPA ruling requires no production or importing of any HCFCs except for use as refrigerants in new equipment produced before 1/1/2020. A small amount (0.5%) is allowed for service between 2020 and 2030.

YEAR

32

Application Guide AG 31-007

What If the United States Reaches the Cap?

The overall goal by the EPA to phase out specific HCFCs as detailed above is to keep the United States within the requirements of the Montreal Protocol. Figure 20 shows the weighted U.S. HCFC anticipated usage and how it should fit within the cap required by the Montreal Protocol. In 1999, the United States reached 95.5% of the cap and has been hovering around that level since. In 1996, it was forecasted that HCFC consumption would approach the cap at the beginning of the millennium but not exceed it and then drop off. Another critical point will come in 2015 when the Montreal Protocol requires a reduction to 10%. The high consumption level prompted the EPA to issue plans for rationing refrigerants if the cap was actually meet. It is anticipated that cap will be reached and allocations will be required. Figure 20 - U.S. HCFC Use and the Montreal Protocol Cap
Millions of kg CFC-11 Equivalent 18 16 14 12 10 8 6 4 2 0 1985 1990 1995 2000 2005 2010 Year 65% - 2004 Revised 2.8% Cap (1995)

35% - 2010 10% - 2015 0.5% - 2020 2015 2020 2025 2030

EPA Proposed Allowance System for HCFCs

In July 2001 the EPA issued 40 CER Part 82, Protection of Stratospheric Ozone; Allowance System for Controlling HCFC Production, Import and Export; Proposed Rule. The final rule has not been published at the time of this publication. Allocation controls occur at the manufacturer, importer, and exporter levels. Parties involved in this business report their activities to the EPA, which then regulates the amounts. The market place is actually familiar with this process because it already does it for Class I (CFCs) substances. Here is a quick list of the requirements;
!

Like the rules for Class I (CFCs) substances, Class II (HCFCs) will have both production and consumption (production + imports - exports) allowances. The allowances are chemical specific. That is, a company will have a production and consumption allowance for R-22 and R-141b etc., measured in kgs of a specific substance. Table 5 shows the allowances for production per company based on the substance. EPA will allocate 100% of the listed individual companies production and consumption baselines. The EPA is reserving the difference in the sum of the all the companies baseline allocations and the United States total cap under the Montreal Protocol for narrow exceptions like a relatively late newcomer to the industry whose baseline is low. The baselines are based on each listed companys highest ODP weighted consumption and production level during the years of 1989, 1994, 1995, 1996 or 1997. The sum of these actually adds up to less than the United States total cap. Allowances can be shifted from one chemical to another by taking into account the ODP weighting. For example an allowance for 10,000 kg of R-142b can be transferred to a 5,909 kg allowance of R-141b. Permanent allowance transfers are also possible. The allocation baseline is set on a one time base year. The baseline is carried forward for each year. It will be reevaluated in 2010 to see if it will meet the requirements of the Montreal Protocol 2010 65% cap reduction.
33

Application Guide AG 31-007

Permanent trades in baseline allocations are allowed. That is, a manufacturer can shift R-123 allocation to R-22. If a company chooses not to produce a substance even though it has an allocation, the EPA does not require the company to give up its allocation for redistribution to other companies. For example, if a company has an allocation for R-123 but chooses not to produce it, the EPA will not require the company to surrender the allocation so that another company can produce the refrigerant. When a phaseout for a specific substance is reached (e.g. R-141b in 2003) all allowances for that substance will cease. Between now and 2004, The EPA will allocate to each allowance holder 100% of their baseline allowance. In 2003, the EPA will subtract the R-141b allowance from all allowance holders. In 2004, if the levels will exceed the 35% Montreal Protocol reduction, the EPA will lower the allocations on each substance on a pro rata basis. In 2010, EPA will reevaluate the baseline levels to ensure the 65% Montreal Protocol reduction is met. In 2015, EPA will reevaluate the baseline levels to ensure the 90% Montreal Protocol reduction is met.
23

! !

Table 5 - Proposed EPA Baseline Production Levels

Company Allied (Honeywell) Ausimont HCFC-22 HCFC-124 HCFC-141b HCFC-142b HCFC-142b HCFC-22 HCFC-123 HCFC-124 HCFC-141b HCFC-142b HCFC-22 HCFC-141b HCFC-142b HCFC-22

Controlled Substance

Allowances (kg) 36,094,556 3,227,086 27,719,366 2,334,508 4,418,767 52,072,484 10,410 6,390 10,464 53,978 22,230,306 23,801,431 15,577,099 2,301,966

Dupont

Elf Atochem (ATOFINA Chemicals) MDA

Each year, the EPA will adjust the production levels as necessary so the United States meets the Montreal Protocol. Each refrigerant will have its production and consumption level adjusted. For instance, a 10% cap will lower the levels for all HCFC refrigerants 10% of their baseline levels. Table 5 lists the proposed production baselines for HCFCs. Table 6 lists the proposed consumption baselines for HCFCs.

23

EPA 40 CFR Part 82 Protection of Stratospheric Ozone; Allowance System for Controlling HCFC Production, Import and Export; Proposed Rule. July 20, 2001
Application Guide AG 31-007

34

Table 6 - Proposed EPA Baseline Consumption Levels

Company ABCO AGA Air systems Allied (Honeywell) Altair Ausimont Automatic Equipment Condor Continental HCFC-22 HCFC-225ca HCFC-225cb HCFC-22 HCFC-124 HCFC-141b HCFC-142b HCFC-22 HCFC-142b HCFC-22 HCFC-22 HCFC-141b HCFC-22 HCFC-123 HCFC-124 HCFC-141b HCFC-142b HCFC-22 HCFC-141b HCFC-142b HCFC-22 HCFC-141b HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-123 HCFC-124 HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-22 HCFC-124 HCFC-141b HCFC-22 HCFC-141b

24

Controlled Substance

Allowances (kg) 253,032 109,653 134,024 32,056,219 2,958,382 18,793,538 1,191,783 241,367 4,418,767 48,989 603,374 18,400 46,599,488 71,063 6,302 8,196 47,820 26,741,356 23,010,714 15,101,025 36,291 73,568 2,306,278 1,837,718 7,776 2,301,966 255,258 4,963,713 76,520 204,980 345,350 41,645 47,180 57,217 34,360 284,370 274,990 3,568,700 43,520 78,720

Dupont

Elf Atochem (ATOFINA Chemicals) HG Refrigeration ICC ICI Kivlan Klomar MDA Mondy-Global National Refrigerants Refricenter Refricentro Rhone-Poulenc R-Lines Saez Solvay Tesco Tulstar

Canada and CFCs

Like the United States, Canada stopped producing and using CFCs in new equipment at the end of 1995. Currently the only source of CFC refrigerants is from reclamation. However, Canada is now developing a strategy for accelerating the phase-out of equipment using CFCs by requiring replacements or conversions to acceptable refrigerants. The goal is to create an orderly transition from CFCs to other more environmentally friendly solutions. Table 7 provides a breakdown of how equipment using CFCs will be phased out.

24

EPA 40 CFR Part 82 Protection of Stratospheric Ozone; Allowance System for Controlling HCFC Production, Import and Export; Proposed Rule. July 20, 2001
35

Application Guide AG 31-007

Table 7 - Existing CFC Phaseout Plan for Canada

Sector Mobile Air Conditioning Mobile Refrigeration Household Appliances Commercial Refrigeration and A/C Approach Prohibit refill with CFCs as soon as possible. Prohibit refill with CFCs effective 2003. Enhance implementation of existing recovery programs; If necessary, add a ban on converting equipment to use CFCs. Staged CFC refill ban effective by year: Equipment < 5 HP: 2004 Equipment <30 HP: 2005 Equipment >30 HP: 2006 Limit releases from low pressure purges to less than 0.1 kg/kg air effective 2003; Require conversion or replacement of CFC-containing chillers at next overhaul effective 2005. Prohibit refill of portable equipment effective 2003;For fixed systems, provide for one refill between 2005 and 2010. The refill would be allowed on the condition that the system is replaced by an alternative within a year of the refill. This would also be subject to critical use exemptions. Starting in 2010, refills will be prohibited.

Chillers

Halons

Canada and HCFCs

Canada has adopted a slightly different plan from the United States in dealing with phasing out HCFCs. The approach is a combination of phasing out HCFC use in areas where other technology is available (the European approach) and phasing out HCFCs with higher ODPs first (The EPA approach). Here are some of the key points; DATE Now July 1999 DETAILS HCFCs cannot be used in areas where it has never been used before. In other words, no new applications using HCFCs can be developed. Containers with 2 kg or less HCFCs cannot be imported or manufactured. Plastic foam where HCFCs were the blowing agent cannot be manufactured or imported (insulation applications are exempt). No cleaning agent using HCFC-141b can be imported or manufactured. Containers with 2 kg or less HCFCs cannot be sold. (There are several exceptions). Polyurethane boardstock where HCFCs were the blowing agent cannot be manufactured or imported (insulation applications are exempt). No cleaning agent using HCFC-141b can be used or sold. HCFC-141b, HCFC-142b and HCFC-22 cannot be manufactured, sold or imported. No equipment that contains these refrigerants is allowed either (Refrigeration applications are exempt). No other HCFC can be manufactured, imported or sold except HCFC-123. HCFC-123 for service only. All HCFCs phased out.

Jan. 2000

Jan 2010

Jan. 2015 Jan 2020 Jan 2030

36

Application Guide AG 31-007

Figure 21 - Canadian Phaseout Schedule for R-22, 141b and 142b

R-22, R-141b, R-142b % Of Cap set by Monteal Protocol 140 120 100 80 60 40 20 0 2000 2005 2010 2015 2020 2025 2030 Year Service Production Only No production R-22, R-141b, R-142b
Cap Set by Montreal Protocol

HCFCs used as refrigerants have different phase out schedule. Figure 21 shows the phaseout for R-22, R-141b and R-142b. From an HVAC point of view, R-22 has the same phaseout as the United States. Figure 22 - Canadian Phaseout Schedule For R-123
R-123 % Of Cap Set by Montreal Protocol 140 120 100 80 60 40 20 0 2000 2005 2010 2015 Year 2020 2025 2030

Cap Set by Montreal Protocol

R-123 Service Production Only No production

Figure 22 shows the Canadian phaseout schedule for R-123 used as a refrigerant. Again it is the same as the United States. Figure 23 - Canadian Phaseout Schedule For Remaining HCFCs
All Other Refrigerants % Of Cap Set by Montreal Protocol 140 120 100 80 60 40 20 0 2000 2005 2010 2015 Year 2020 2025 2030 No production
Cap Set by Montreal Protocol

All Other Refrigerants

Figure 23 shows the phase out schedule for any other HCFCs used as refrigerants. This is slightly different than the United States but most HVAC products use one of the refrigerants listed above.

Application Guide AG 31-007

37

Europe
Figure 24 - EC HCFC Phaseout Schedule Europe also stopped using CFCs at the end of 1995. It is not as dependent on HCFC 120 usage as North America and EU 2008 - 35% 100 Production so has taken a more 2014 - 20% 80 aggressive stance on phasing 2020 - 15% 60 out HCFCs. The European 2025 - No 40 Production Community (EC) has 20 developed a phase out plan 0 for HCFCs that exceeds the 1990 1995 2000 2005 2010 2015 2020 2025 2030 requirements of the Montreal Year Protocol. Many European phaseout policies are based on application as well as substance. For instance HCFC usage as a refrigerant can have one phaseout schedule while HCFC usage as a blowing agent another.
EU Production

Figure 24 shows the phase-out scheduled in Council regulation 300R2037. The EC has committed to review HCFC production with an eye to a production cut in advance of 2008 and whether the levels for 2008, 2014 and 2020 should be lowered. Many European countries have adopted legislation that exceeds the requirements of the EC. Figure 25 shows the accelerated phaseout schedules (beyond EC 300R2037) for several European countries. Figure 25 - Accelerated HCFC Refrigerant Phaseout Schedule for European Countries
Norway Jan 1, 1999 phaseout in new refrigerating equipment Netherlands Jan 1, 1999 phaseout in new refrigerating equipment United Kingdom Following EC Plan Ireland Following EC Plan

% of Cap Set by Montreal Protocol

Finland Jan 1, 2000 phaseout in new refrigerating equipment Sweden 1995 Phaseout Service allowed to 2002 Denmark Jan 1, 2000 phaseout in new refrigerating equipment Germany Jan 1, 2000 phaseout in new refrigerating equipment Austria Jan 1, 2000 phaseout in new refrigerating equipment

Belgium Following EC Plan France Following EC Plan

Portugal Following EC Plan

Spain Following EC Plan

Greece Following EC Plan Italy Jan 1, 2009 Phaseout

38

Application Guide AG 31-007

Several European countries are receptive to using hydrocarbons and other flammable refrigerants, particularly in domestic applications such as refrigerators. The trend is for countries to the north to use less HCFCs and more flammable substances. Some countries such as Denmark have legislation ready to phase out HFCs as well.

Montreal Protocol and EPA on HFCs

HFCs do not affect the ozone layer. They have an ODP = 0. Both the Montreal Protocol and the EPA have no restrictions on the use of HCFS nor do they have any phase requirements for HFCs. This is one of the main reasons that HFCs such as R-134a, have risen to such prominence as refrigerants in the last few years.

Climate Change and Refrigerants

Climate Change, sometimes referred to as global warming, is the second major environmental challenge to face the HVAC industry. The Earth is warmed by incoming solar radiation from the sun. The Earth and the gases in the atmosphere absorb about 2/3 of the incoming radiation. The remaining 1/3 is reflected back by cloud cover, airborne particles and the Earths surface mostly as infrared radiation. Certain gases in the atmosphere can trap that energy and stop it from escaping. This raises the Earths mean temperature. The process is often referred to as the greenhouse effect and the gases that can trap the energy are referred to as greenhouse gases (GHGs). While some trapping of heat is desired, too much can cause the Earth to become too warm. Scenarios such as polar ice caps melting with wide spread flooding are an extension of this problem. The long time line for climate change events also makes it difficult to evaluate the problem. Climate change happens naturally over many thousands of years (ice ages for example). Modern science has been collecting data only for a very short time period making it very difficult to ascertain any trends. While the greenhouse process is an accepted scientific model, there are many mechanisms connected with the process are that are not as clear and are seriously debated. For instance, a raising of the Earths mean temperature should produce more evaporation of ocean water and hence more cloud cover. The cloud cover could reduce the incoming solar radiation offset the greenhouse effect. There is enough concern that the ASHRAE Position Paper on Climate Change25 suggests global average surface temperatures could rise by 1.8 to 6.3F by 2100 with a corresponding rise in sea levels of 6 to 37 inches by the end of the next century. What is understood is that too much global warming is a serious problem and greenhouse gases play a key role in the process. Another way to look at it is that there are no plausible scientific models that dispel the greenhouse gas global warming model. What is being debated is the severity of the change in climate. There is enough data that the Intergovernmental Panel on Climate Change (IPCC) under the United Nations Framework Convention on Climate Change (UNFCCC) reported in 1995 that the balance of evidence suggests a discernable human influence on global climate. This led to the Kyoto Protocol.

25

Climate Change: Position Paper. Approved by the Board Of Governors, June 24, 1999. ASHRAE, Atlanta Ga.
39

Application Guide AG 31-007

Greenhouse Gases Including Carbon Dioxide

Many substances are greenhouse gases, including methane, nitrous oxide, chlorofluorocarbons (CFCs) hydrochlorofluorocarbons (HCFCs), Hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF6) and carbon dioxide (CO2). CFCs, HCFCs and HFCs represent most of the substances used for refrigerants in the world today. Much of the electrical power used to operate refrigeration systems comes from the burning of fossil fuels, which emit CO2, which is also a greenhouse gas. Figure 26 - Breakdown of Greenhouses Gases
600 500 400 ppm 300 200 100 0 -100 2000 2020 CO2 N2O + CH4 Cl, Br, F species all refrigerants 2040 YEAR 2060 2080 2100 total
26

Figure 26 shows a breakdown of substances that contribute to climate change based on equivalent carbon dioxide concentrations. The common scale used to measure greenhouse gases is to equate greenhouse gases to carbon dioxide either as carbon dioxide equivalent concentration measured in parts per million (ppm) or as Global Warming Potential (GWP).

GWPs are based the relative warming effect a similar mass of carbon dioxide would have typically over a 100 year period. Table 1 lists the GWP for many common refrigerants. Carbon dioxide is used as reference because it has the single largest impact of any one greenhouse gas.

Carbon Dioxide Levels

Changes in carbon dioxide levels since the start of the industrial revolution are documented and alarming. Based on ice core samples the CO2 concentration 150 years ago was 270 ppm. Today, the level has climbed to 370 ppm. Even if the Kyoto Protocol is adopted and there is steady energy efficiency improvements, there are predictions27 that the CO2 level will double by 2050, triple by 2100 and quadruple by 2150. The main source of CO2 is the burning of fossil fuels for energy. It is estimated that in North America, 1/3 of the energy consumed is used in buildings. Energy efficient buildings will have a direct and major affect on CO2 emissions.

Direct and Indirect Affects of Refrigerants

Refrigerants affect climate change in two ways. The first way is when released directly into the atmosphere. Most of the refrigerants in use today have some level of GWP. Some are very high. The good news is the actual amount of refrigerants released to the atmosphere is very small (especially when compared to CO2 emissions) and so the overall direct effect is limited. Over the period 20002100, CFC, HCFC and HFC refrigerant manufacture and emissions will account for only 3% of the total climate forcing due to long-lived anthropogenic greenhouse gases.28

Frasier, P. 1998. Refrigerants: contributions to climate change and ozone depletion. AIRAH Journal, June 1998 27 Mahlman, J., Speaking at ASHRAE 2001 Winter Meeting. Response to global warming will affect its severity. ASHRAE Journal. March 2001. 28 Frasier, P. 1998. Refrigerants: contributions to climate change and ozone depletion. AIRAH Journal, June 1998
40 Application Guide AG 31-007

26

The second way refrigerants affect climate change is indirect and deals with system efficiency. In many cases the energy used to operate a refrigeration system comes from the burning of fossil fuels. The carbon dioxide released in this process affects climate change. The more efficient the refrigeration system, the less carbon dioxide released.

TEWI
TEWI stands for Total Equivalent Warming Impact. It is the sum of the effect of a direct discharge of refrigerant plus the effect of carbon dioxide emissions due to energy use over the lifetime of the equipment. TEWIs are based on carbon dioxide which has a GWP =1.0. The refrigerant portion is converted to the amount of carbon dioxide that would have an equivalent affect and then added to the power station emissions also in carbon dioxide. The impact can exceed the life time of the equipment so it is necessary to choose a timeline to consider the effects. An Integrated Time Horizon (ITH) of 100 years is often used. Because the two parts that make up TEWIs are based on the system, it is not possible to obtain a TEWI for a particular refrigerant. Leakage rates and refrigeration system efficiency are not properties of the refrigerant itself. Figure 27 - TEWI For Chillers
29

TEWI for 1000 Ton Chiller in Atlanta

4 % charge loss/year

R123 R134a R22 R 717

Refrigerant

R123 R134a R22 R 717 R123 R134a R22 R 717 R123 R134a R22 R 717

2 % charge loss/year

1 % charge loss/year

Energy Emissions Refrigerant Emissions

Figure 27 shows the TEWI for a 1000 ton chiller in Atlanta.30 From these tables, it can be seen that refrigerant emissions is less than 5% of the total TEWI. Recently, there has been a movement to take an even more holistic look at energy and environmental impact. The Term Life Cycle Warming Impact or LCWI has been used to discuss a cradle-to grave-approach that

0.5 % charge loss/year

10000000

20000000 30000000

40000000

TEWI (kg CO2)

includes the energy cost to manufacture the system.

Refrigerant Emissions
To control the effect that refrigerants have on climate change, it is critical to control refrigerant emissions to the atmosphere. This goes beyond leaks to include servicing and reclamation at the end of the equipment life.

Energy Consumption
Based on Figure 27 it can be seen that energy efficiency is the most critical issue for refrigerants and climate change. It goes beyond just full load performance but must include the part load performance over the life of the equipment.

29

Baxter,V., S. Fischer, J Sand. September 1998. Global Warming Implications of Replacing OzoneDepleting Refrigerants. ASHRAE Journal. Atlanta Ga. 30 Baxter,V., S. Fischer, J Sand. September 1998. Global Warming Implications of Replacing OzoneDepleting Refrigerants. ASHRAE Journal. Atlanta Ga.
Application Guide AG 31-007 41

Kyoto Protocol
Background
In 1990, the United Nations established a committee to form a framework on Climate Change. In May 1992, the countries at the Rio de Janeiro Earth Summit adopted the agreement. Since then, over 176 countries (including the United States) have ratified it. The agreement established a process where countries could meet (known as a Conference of parties or COP) and discuss the formation of an international legal agreement or Protocol. The first COP-1 was held in Berlin. In 1997, the third COP meeting was held in Kyoto, Japan where the Kyoto Protocol was approved. The Kyoto Protocol enters into force when at least 55% of the countries representing at least 55% of the annex 1 1990 carbon dioxide equivalent emissions have ratified it. To date, 13 countries have ratified the Protocol. The United States has not.

Kyoto Protocol Requirements

The Kyoto Protocol is intended to reduce the Annex 1 (developed countries) carbon dioxide emissions by 5.2% from the 1990 levels based on the emissions from 2008 to 2012. Each Annex 1 country has its own target as shown in Table 8. Table 8 - Carbon Dioxide Emissions Reductions by Country
Country Australia Austria Belgium Bulgaria Canada Croatia Czech Republic Denmark Estonia European Community Finland France Greece Hungary Iceland Ireland Italy Japan Latvia Percent Reduction +8 8 8 8 6 5 8 8 8 8 8 8 8 6 +10 8 8 6 8 Country Liechtenstein Lithuania Luxembourg Monaco Netherlands New Zealand Norway Poland Portugal Romania Russian Federation Slovakia Slovenia Spain Sweden Switzerland Ukraine United Kingdom United States Percent Reduction 8 8 8 8 8 0 +1 6 8 8 0 8 8 8 8 8 0 8 7

The reductions required in Table 8 are real a challenge for most countries because their emission levels have increased since 1990. The United States for example, is expected to see a 34% growth in emissions during this period, requiring a 41% overall reduction. Only Germany and the United Kingdom are on track to meet their goals. The Kyoto Protocol does not specify how a country should obtain the emissions level. This is left up to the individual country. The European community wanted stronger requirements.

42

Application Guide AG 31-007

Targeted Gases
There are 6 greenhouse gases covered by the Kyoto Protocol. These are carbon dioxide, methane (CH4), nitrous oxide (N2O), HFCs, perfluorocarbons (PFCs) and sulfur hexafluoride (SF6) (with a GWP of 23,900). Although CFCs and HCFCs are greenhouse gases, they are not included because they are being phased out by the Montreal Protocol. The baseline year each country is to use for carbon dioxide, methane and nitrogen oxide is 1990. Each country has the choice of setting the base level for HFCs, PFCs and SF6 on either 1990 or 1995 levels. The emissions for all these gases are added up for each country in what is referred to as a basket. There are no requirements by the Kyoto Protocol to stop using any of these substances. The only requirement is to reduce their combined emissions to the target countrys target. This is a very important difference between the Kyoto Protocol and the Montreal Protocol where specific substances were to be phased out of production and use.

Sinks
The Kyoto Protocol allows for sinks. Forests, soil and land use can absorb carbon dioxide and thus lower the emissions from a particular country. Accounting for sinks is difficult, but was fundamental in getting the protocol passed.

Emissions Trading
The protocol allows for emissions trading among annex I parties. The actual mechanism has not been agreed upon but a country must have emission reduction projects within its borders and may not achieve all its reductions by emissions trading.

Clean Development Mechanism

The clean development mechanism (CDM-Article 12) allows annex I countries to fund emissions reductions projects in developing countries and get credit towards their own emissions reduction. The details of the mechanism have not been worked out.

Developing Countries
Developing or Annex II countries are not currently covered by the Kyoto Protocol. This is important for several reasons. The United States is not expected to ratify the Protocol until there are provisions for developing countries. The concern is the United States would be put into an economic disadvantage. Since the United States is the largest carbon dioxide emitter, it is unlikely that the Kyoto Protocol can be ratified without its support. The second issue with developing countries is their significant increase as carbon dioxide emitters. Currently, the United States emits 4,881,000 metric tons equivalent carbon dioxide. China, an annex II country, produces 2,667,000 metric tons and is expected to surpass the United States in the next 15 years.

Montreal and Kyoto Protocols

The Montreal and Kyoto protocols are tied together in many ways. In some circumstances, they appear to be in conflict with each other. There is also data and scientific theories that indicate ozone depletion and global warming are physically tied together. The Montreal Protocols regulatory approach is to phase out consumption and use of ozone depleting substances such as CFCs and HCFCs. The Kyoto Protocol regulates reduced emissions of gases included in the basket (including HFCs). Ozone depletion and climate change phenomena are also interrelated. Global warming tends to raise the troposphere (lower atmosphere) which cools the stratosphere (upper atmosphere). A colder stratosphere increases PSCs which leads to ozone depletion (see Why Antarctica?, page 29).

Application Guide AG 31-007

43

Refrigerants in The Future

In the mid-nineties, the HVAC and R industry went through a huge change as the requirements of the Montreal Protocol phased out CFCs. Many then unheard of refrigerants (R-134a and R-123) came to the forefront as replacements for old standbys like R-12 and R-11. The Industry is on the cusp of another change as the HCFCs start to be phased out (R-22 will be phased out by 2010 in the United States) and effects of Kyoto Protocol start being felt. Despite the wide range of refrigerants available, only a few are under serious consideration. This section will look at the choices and offer some speculation on the outcome.

Water (R-718)
Water is the refrigerant in absorption chillers. It is non toxic, abundant, non-flammable and has no ODP or GWP. The main drawback is the efficiency on absorption chillers. The current commercial double effect, direct fired (operates on natural gas) chiller has a COP=1. Compare this with centrifugal chillers with COPs of 6.4 or better. A comparison of TEWIs for an absorption chiller and an electric centrifugal is the best way to decide which is the best with regards to climate change. The TEWI will depend on how the electrical power is generated. Prediction Absorption chillers will continue to see niche applications (Cogen and hybrid plants) in North America. If energy rates change enough (a possibility with deregulation) then absorption chillers may take on a larger role.

In markets such as Japan, absorption chillers are the norm and centrifugal chillers are the exception. In North America, absorption chillers cost approximately twice as much as electric centrifugal chillers and often cost more to operate, making them difficult to justify.

Ammonia (R-717)
Ammonia has excellent performance, no ODP and a small GWP. However, the health and flammability issues surrounding ammonia have limited it to industrial and controlled commercial applications.

Prediction Ammonia will continue to see industrial and controlled commercial applications.

Carbon Dioxide (R-744)

Carbon dioxide is non-toxic, non-flammable and has no ODP and a low GWP. Its low critical point, however, makes it a poor performer at typical commercial operating conditions. As well, the operating pressures are very high (900 psig). Research is underway to study carbon dioxide at trans-critical conditions. As well, it has been used successfully in cascade refrigeration systems. Prediction Possible future applications in automotive air conditioning and cascade refrigeration plants.

Propane (R-290) and Isobutane (R-600a)

Propane and isobutane have low toxicity, good performance, no ODP and low GWP. However, they are flammable. Northern Europe has accepted them in refrigerators. CocaCola has announced it will move away from HFCs and has considered flammable refrigerants. In the United States, there are strong concerns about safety with respect to flammability. Prediction Flammable refrigerants will most likely continue to see use in the domestic and small system market.

44

Application Guide AG 31-007

There have been studies performed evaluating the efficiency of flammable refrigerants where brine is cooled and then pumped to where cooling is required (as opposed to direct DX cooling). These reports show propane and isobutane as less efficient than traditional direct cooling R-22 systems. However this should be understood in light of the use of brine. There are only a handful of large capacity installations in the world.

R-134a
R-134a is classified as an A1 (Lower toxicity no flame propagation) refrigerant by ASHRAE, it has no ODP but the GWP is 1300. It has very good performance, heat transfer properties and is a good candidate for screw and centrifugal compressor applications. Its acceptance in the automotive industry makes it very abundant. R-134a appears to be caught between the Montreal and Kyoto Protocols. The Montreal Protocol is systematically removing from service common refrigerant with ODP> 0. By default, the protocol is driving the market to refrigerants with ODP=0 such as R-134a. On the other hand, the Kyoto protocol has put HFCs in the basket of targeted gases. R-134a is one of the best solutions available. It has 0 ODP and therefore has no phaseout date from the Montreal Protocol. Although HFCs are in the Kyoto Basket, only its emissions are regulated. There is no phase out Prediction date for HFCs. While CFCs and HCFCs are major R-134a will continue to be the contributors to ozone depletion (28% of anthropogenic ozone main large capacity refrigerant depletion), HFCs, CFCs and HCFCs direct effect is only a in the HVAC industry for the minor player in climate change (4% of anthropogenic global foreseeable future. warming). All second generation centrifugal and screw chillers in the market place have been designed around R-134a.

Replacements for R-22

R-22 is classified as an A1 (Lower toxicity no flame propagation) refrigerant by ASHRAE. It is the most popular refrigerant in the world. R-22 is also an HCFC and as such is being phased out. In the United States, R-22 is already capped and will be completely phased out in 2010 except small a amount for service. R-22 is extremely versatile. It is used in supermarket refrigeration, skating rinks, chillers with all types of compressors, packaged rooftop units and most residential air conditioning. There are no direct replacements for R-22. Different refrigerants will end up replacing various applications of R-22. Table 9 lists several replacements and their relative performance to R-22. Figure 28 shows the COP of the replacement refrigerants at a 130 F condensing temperature31. Table 9 - Relative Performance of R-22 Replacements
R-290 Capacity Efficiency Suction Press, abs Cond Press, abs Glide 85% 99% 94% 90% 0 R-134a 67% 100% 59% 68% 0 R-404A 106% 93% 121% 120% 1F R-407C 95% 98% 91% 115% 8F R-410A 141% 100% 159% 157% 1F R507 109% 94% 125% 122% 0

31

Meyer, J. 2000. Experimental Evaluation of Five Refrigerants as Replacements For R-22. ASHRAE MN-00-6-4
45

Application Guide AG 31-007

Figure 28 - COP of R-22 Replacements

Cololing coefficient of perfomance at condensing tempertures of 55 C
4 3.5 3 2.5 2 1.5 1 0.5 0 -20 -10 0 10 20 Evaporating temperature

Coling COP

R-134a R-290 R-22 R-410a R-404c R-407c

The use of R-22s in centrifugal chillers has always been limited and for the most part that sector has moved to R-134a. R-22s use in screw chillers (water and air-cooled) is now moving to R-134a for the most part. All second-generation screw compressors have been developed to work with R-134a. R404A and R-507 are being used in refrigeration applications previously performed by R-22.

This leaves all the small compressor applications including package rooftop units, small air and water cooled chillers (under 200 tons) and the entire residential air conditioning (multi-billion dollar) industry. The two main candidates are R407C and R-410A. Propane (R-290) can be used in the residential market, but the concerns about flammability in North America have severely limited its application.

R-407C
R-407C is a zeotropic blend of HFC-32, HFC-125 and HFC-134a. Its properties have been tuned to be very close to R-22 but it has a glide of over 8F. R-407C can be dropped into an existing R22 refrigeration system and work although often with some performance loss. In many applications, the performance can be improved with minor changes to the refrigeration system sub-components (for example adding Prediction condenser surface area). R-407C will be used as a drop in replacement for R-22 in The high glide limits its applications to only to DX units such existing systems and as an as rooftop units and some chillers where glide is less of an interim solution for existing issue. R-407C is often considered a replacement drop in product lines until new lines refrigerant to be used in upgrading existing systems to an HFC are developed. refrigerant. There is limited new generation product development based on R-407C.

R-410A
R-410A is a zeotropic blend of HFC-32 and HFC-125. It has a minimal glide (less that 1F) and a very low volume flowrate (1.5 cfm/ton). It also operates at higher pressures than R-22 (450 psi). It cannot be dropped into an existing R-22 system but instead must be used in a new generation design. There is a lot of interest in R-410A as the new generation replacement for R-22 with smaller systems. Compressor manufacturers have started to offer small (1/2 to 5 ton) compressors designed for R410A, which has led to its introduction in the residential market (Carrier refers to residential R-410A systems as Pureon). As larger compressors become available, R-410A will spread into more commercial products. With the Prediction higher operating pressures associated with R-410A, all subAs more refrigeration sub components (valves, sight glasses, filterdriers etc) need to be components become available, redesigned, which has slowed R-410As launch into the next generation residential and commercial market place. light commercial products will One issue with R-410A is the low critical point and applications in high ambient. This significantly reduces the performance of air cooled equipment in hot locations. Watercooled equipment is generally unaffected because of the lower condensing temperatures. utilize it. Some technology will be implemented to address the low critical point issue.

46

Application Guide AG 31-007

Replacements for R-123

ASHRAE Standard 34 classifies R-123 as a B1 refrigerant (higher toxicity no flame propagation). It is the HCFC replacement for CFC-11 and as such is being phased out. In the United States, R-123 is already capped and will be reduced to 0.5% production in 2020 for service only until 2030. R-123 is used almost exclusively in negative pressure centrifugal chillers. There is no clear replacement for R-123. Possible use of R-601 (n-pentane) or R-601a (isopentane) is unlikely. These are both highly flammable. The required charge levels used in centrifugal chillers would make an explosion possible. As well, negative pressure chillers draw in air allowing an explosive mixture to be present in the chiller. Figure 29 Vapor Pressure of Low-pressure Refrigerants The two closest HFCs are R245ca and R-245fa (they are isomers same atoms but 60 different configuration). 50 Most of the early work was CFC-11 40 centered around R-245ca HFC-245fa 30 until it was found that it was 1 Atmosphere 20 flammable. R-245fa is a B1 15 psig 10 refrigerant (higher toxicity no flame propagation). It 0 also operates at higher pressures than R-123. Temperature - F Where R-123 does not require ASME rated shells (at normal conditions), R-245fa will require ASME rated condensers (See Figure 2932). R-245fa cannot be a replacement for existing R-123 chillers unless the chiller is ASME rated.
Pressure vs. Temperature
Pressure - psia 100 110

To refrigerant manufacturers, R-123 use in negative pressure centrifugal chillers is a small market. Fortunately, R-123 can be manufactured as a byproduct from manufacturing other more common refrigerants. R-245fa is a more expensive refrigerant to manufacture. Its realistic introduction into the market place would require other applications for the substance (e.g. foam blowing) to get the production quantities large enough to get the cost down.

120

10

20

30

40

50

60

70

80

90

Prediction R-123 will be used in negative pressure chillers until it is phased out by the Montreal Protocol. There is some speculation that there may be an exemption for R-123 for refrigeration use, but that is unlikely. It would require a majority vote of the Montreal Protocol members. With its limited use outside the United States and other technologies available a change in the Protocol is extremely unlikely. Possible retrofit kits for existing R-123 chillers with R245fa may be available but only if the shells are ASME rated.

32

Hughes, H.M. Contemporary Fluorocarbons. 1997. Refrigerants For the 21st Century. ASHRAE. Atlanta, Ga.
47

Application Guide AG 31-007

Conclusions
Because refrigerants are interwoven with major environmental concerns, they will be a major factor in the decision making process for air conditioning and refrigeration. This is true not only for equipment manufacturers, but also for HVAC engineers. At a minimum, when comparing systems and all other technical issues are balanced, refrigerant selection will tip the scales one way or the other. In many applications, refrigerants will have a much larger influence in the decision making process. Although refrigerants only make up 3 to 4 % of the climate change problem directly, the energy consumed in by refrigeration systems will put the spot light on efficient refrigeration system design. Refrigerant selections that meet all other criteria but offer poor performance will not help the environment. The imminent phase out of R-22 will again bring refrigerants to the forefront requiring the HVAC industry to provide guidance to decision makers everywhere. A similar discussion will occur as the phase out for R-123 approaches. A strong understanding of the material covered in this guide will certainly help. For more information please contact your McQuay Sales Representative or McQuay at www.mcquay.com.

48

Application Guide AG 31-007

References
1998 ASHRAE Refrigeration Handbook ASHRAE. Atlanta, Ga 2001 ASHRAE Fundamentals Handbook ASHRAE. Atlanta, Ga An Environmental Rationale For Retention of Endangered Chemicals Wuebbles, D.,J. Calm. Science, Volume 278.November 7, 1997. American Association for the Advancement of Science. ANSI/ASHRAE Standard 34-1997, Designation and Safety Classification of Refrigerants. ASHRAE. Atlanta, Ga. ASHRAE Technical Data Bulletin CFC Alternatives: Characteristics and Applications, Volume 8, Number 1 1992. ASHRAE. Atlanta, Ga ASHRAE Technical Data Bulletin Dealing with Used Refrigerants in the 90s, Volume 9, Number 5 1993. ASHRAE. Atlanta, Ga Climate Change: Position Paper - Approved by the Board Of Governors, June 24, 1999. ASHRAE, Atlanta Ga. Compatibility of Refrigerants and Lubricants With Elastomers. Final Report No. DOE/CE 23810-14 - Haned, G.R. and R.H. Seiple. 1993. ARTI Database. Air-conditioning and refrigeration Technology Institute, Arlington, Va. Developing the Hydrofluorocarbon Range: Fluids for Centrifugal Chillers - Corr, S., J.D. Morrison, F.T. Murphy and R.L. Powell, 1995. Proceedings of the 19th International Congress of Refrigeration, IIR. Paris, France Experimental Evaluation of Five Refrigerants as Replacements For R-22 - Meyer, J. 2000. ASHRAE MN-00-6-4 Experimental Study on Fractionation of R-407C and Recharge Operations Paulas-Lanckriet, M., O. Buyle .July, 1998. International refrigeration Conference at Purdue. Global Warming Implications of Replacing Ozone-Depleting Refrigerants - Baxter,V., S. Fischer, J Sand. September 1998. ASHRAE Journal. Atlanta Ga. IPCC Report. 1995: NIST Standard Reference Database 23 - Version 6.01 (NIST 1996). Ozone Depleting Substances: Position Paper - Approved by the Board Of Governors, Feb. 1, 2001. ASHRAE, Atlanta Ga. Quest for Alternatives - McLinden, M.O., and D. A. Didion. 1987. ASHRAE Journal 29, Atlanta Ga. Reactions of Chlorofluoro-Hydrocarbons with Metals - Eiseman, B.J. 1963. ASHRAE Journal 5(5):63 Refrigerant Safety - Calm, J. ASHRAE Journal, July 1994. ASHRAE. Atlanta Ga. Refrigerant Selection Guide June 1998. AIRAH Refrigerants For the 21st Century - 1997. ASHRAE. Atlanta, Ga. Refrigerants: Contributions to Climate Change and Ozone Depletion - Frasier, P. 1998. AIRAH Journal, June 1998 Stratospheric Sink for Chlorofluoromethanes: Chlorine-atom catalyzed destruction of ozone Molina, M., F.S. Rowland. 1974. Nature 249 Successes in the fight to save ozone layer could close hole by 2050 - Schrope, M. Dec. 7, 2000.. Nature V408. The Relative Efficiency of a Number of Halocarbons for Destroying Stratospheric Ozone Wuebbles, D.J. 1981.. Report UCID-18924, Livermore, Ca; Lawrence Livermore National Laboratory (LLNL) Trade-offs in Refrigerant Selections: Past, Present and Future Calm, J., D. Didion. 1997. ASHRAE. Atlanta, Ga.

Application Guide AG 31-007

49

Websites
www.ARI.org www.ASHRAE.org www.ashraejournal.org www.doe.gov www.dupont.com www.ec.gc.ca www.epa.gov www.ARTI-21cr.org www.atofinaChemicals.com www.iiar.org www.un.org www.ipcc.ch Air-conditioning and Refrigeration Institute American society of Heating Air-conditioning and Refrigeration Engineers. Direct Link to ASHRAEs monthly Journal Magazine U.S. Department of Energy Dupont, Manufacturer of refrigerant Environment Canada U.S. Environmental Protection Agency ARTI is the research group for ARI Atofina, Manufacturer of refrigerants International Institute of Ammonia Refrigeration United Nations Intergovernmental Panel on Climate Change. Joint group set up by United Nations and World Meteorological Organization. European refrigerant policy McQuay International International Institute of Refrigeration National Institute of Standards and Technology

www.europa.eu.int www.mcquay.com www.iifiir.org www.NIST.gov

50

Application Guide AG 31-007

Appendix 1 R-134a MSDS Sheet

Information in this format is provided as a service to our customers and is intended only for their use. Others may use it at their own discretion and risk. The MSDS format adheres to U.S. standards and regulatory requirements and may not meet regulatory requirements in other locations. This information is based upon technical information believed to be reliable. It is subject to revision as additional knowledge and experience are gained. Please return to this website for the most current version.

"DYMEL" 134a
6001FR Revised 17-AUG-2001

CHEMICAL PRODUCT/COMPANY IDENTIFICATION

Material Identification "DYMEL" is a registered trademark of DuPont. Corporate MSDS Number CAS Number Formula CAS Name Tradenames and Synonyms CC0050 Company Identification MANUFACTURER/DISTRIBUTOR DuPont Fluoroproducts 1007 Market Street Wilmington, DE 19898 PHONE NUMBERS Product Information Transport Emergency Medical Emergency : 1-800-441-7515 (outside the U.S. 302-774-1000) : CHEMTREC 1-800-424-9300(outside U.S. 703-527-3887) : 1-800-441-3637 (outside the U.S. 302-774-1000) : : : : DU000693 811-97-2 CH2FCF3 1,1,1,2-TETRAFLUOROETHANE

Application Guide AG 31-007

51

COMPOSITION/INFORMATION ON INGREDIENTS
Components Material ETHANE, 1,1,1,2-TETRAFLUORO(HFC-134a) CAS Number 811-97-2 % 100

HAZARDS IDENTIFICATION
Potential Health Effects INHALATION ETHANE, 1,1,1,2-TETRAFLUOROGross overexposure may cause: Central nervous system depression with dizziness, confusion, incoordination, drowsiness or unconsciousness. Irregular heart beat with a strange sensation in the chest, "heart thumping", apprehension, lightheadedness, feeling of fainting, dizziness, weakness, sometimes progressing to loss of consciousness and death. Suffocation, if air is displaced by vapors. SKIN CONTACT ETHANE, 1,1,1,2-TETRAFLUOROImmediate effects of overexposure may include: Frostbite, if liquid or escaping vapor contacts the skin. EYE CONTACT ETHANE, 1,1,1,2-TETRAFLUORO"Frostbite-like" effects may occur if the liquid or escaping vapors contact the eyes. ADDITIONAL HEALTH EFFECTS ETHANE, 1,1,1,2-TETRAFLUOROIncreased susceptibility to the effects of this material may be observed in persons with pre-existing disease of the: central nervous system, cardiovascular system. Carcinogenicity Information None of the components present in this material at concentrations equal to or greater than 0.1% are listed by IARC, NTP, OSHA or ACGIH as a carcinogen.

FIRST AID MEASURES

First Aid INHALATION
Application Guide AG 31-007

52

If high concentrations are inhaled, immediately remove to fresh air. Keep person calm. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Call a physician. SKIN CONTACT In case of contact, immediately flush skin with plenty of water for at least 15 minutes, while removing contaminated clothing and shoes. Call a physician. Wash contaminated clothing before reuse. Treat for frostbite if necessary by gently warming affected area. EYE CONTACT In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Call a physician. INGESTION Ingestion is not considered a potential route of exposure. Notes to Physicians Because of possible disturbances of cardiac rhythm, catecholamine drugs, such as epinephrine, should only be used with special caution in situations of emergency life support.

FIRE FIGHTING MEASURES

# Flammable Properties Flash Point : No flash point

Flammable Limits in Air, % by Volume: LEL : None per ASTM E681 UEL : None per ASTM E681 Autoignition : >743 C(>1369 F) Fire and Explosion Hazards: Cylinders may rupture under fire conditions. may occur. Decomposition

Contact of welding or soldering torch flame with high concentrations of refrigerant can result in visible changes in the size and color of torch flames. This flame effect will only occur in concentrations of product well above the recommended exposure limit, therefore stop all work and ventilate to disperse refrigerant vapors from the work area before using any open flames. HFC-134a is not flammable in air at temperatures up to 100 deg. C (212 deg. F) at atmospheric pressure. However, mixtures of HFC-134a with high concentrations of air at elevated pressure and/or temperature can become combustible in the presence of an ignition source. HFC-134a can also become combustible in an oxygen enriched environment (oxygen concentrations greater than that in air). Whether a mixture containing HFC-134a and air, or HFC-134a in
Application Guide AG 31-007

53

an oxygen enriched atmosphere become combustible depends on the inter-relationship of 1) the temperature 2) the pressure, and 3) the proportion of oxygen in the mixture. In general, HFC-134a should not be allowed to exist with air above atmospheric pressure or at high temperatures; or in an oxygen enriched environment. For example HFC-134a should NOT be mixed with air under pressure for leak testing or other purposes. Experimental data have also been reported which indicate combustibility of HFC-134a in the presence of certain concentrations of chlorine. Extinguishing Media Use media appropriate for surrounding material. Fire Fighting Instructions Cool tank/container with water spray. Self-contained breathing apparatus (SCBA) may be required if cylinders rupture or release under fire conditions. Water runoff should be contained and neutralized prior to release.

ACCIDENTAL RELEASE MEASURES

Safeguards (Personnel) NOTE: Review FIRE FIGHTING MEASURES and HANDLING (PERSONNEL) sections before proceeding with clean-up. Use appropriate PERSONAL PROTECTIVE EQUIPMENT during clean-up. Ventilate area, especially low or enclosed places where heavy vapors might collect. Remove open flames. Use self-contained breathing apparatus (SCBA) if large spill or leak occurs.

HANDLING AND STORAGE

Handling (Personnel) Use with sufficient ventilation to keep employee exposure below recommended limits. Handling (Physical Aspects) HFC-134a should not be mixed with air for leak testing or used for any other purpose above atmospheric pressure. See Flammable Properties section. Contact with chlorine or other strong oxidizing agents should also be avoided. Storage Store in a clean, dry place. Do not heat above 52 C (126 F).

54

Application Guide AG 31-007

EXPOSURE CONTROLS/PERSONAL PROTECTION

Engineering Controls Normal ventilation for standard manufacturing procedures is generally adequate. Local exhaust should be used when large amounts are released. Mechanical ventilation should be used in low or enclosed places. Refrigerant concentration monitors may be necessary to determine vapor concentrations in work areas prior to use of torches or other open flames, or if employees are entering enclosed areas. Personal Protective Equipment Impervious gloves and chemical splash goggles should be used when handling liquid. Under normal manufacturing conditions, no respiratory protection is required when using this product. Self-contained breathing apparatus (SCBA) is required if a large release occurs. Exposure Guidelines Exposure Limits "DYMEL" 134a PEL (OSHA) TLV (ACGIH) AEL * (DuPont) WEEL (AIHA)

: : : :

None None 1000 1000

Established Established ppm, 8 & 12 Hr. TWA ppm, 8 Hr. TWA

* AEL is DuPont's Acceptable Exposure Limit. Where governmentally imposed occupational exposure limits which are lower than the AEL are in effect, such limits shall take precedence.

PHYSICAL AND CHEMICAL PROPERTIES

Physical Data Boiling Point Vapor Pressure Vapor Density % Volatiles Solubility in Water Odor Form Color Liquid Density Specific Gravity : : : : : : : : : : -26.5 C (-15.7 F) @ 736 mm Hg 96 psia @ 25 C (77 F) 3.6 (Air=1.0) @ 25 C (77 F) 100 WT% 0.15 WT% @ 25 C (77 F) @ 14.7 psia Ether (slight). Liquified Gas. Colorless. 1.21 g/cm3 @ 25 C (77 F) 1.208 @ 77 F (25 C)

Evaporation Rate : (CCL4 = 1); greater than 1

Application Guide AG 31-007

55

STABILITY AND REACTIVITY

Chemical Stability Stable. Conditions to Avoid Avoid open flames and high temperatures. Incompatibility with Other Materials Incompatible with alkali or alkaline earth metals - powdered Al, Zn, Be, etc. Decomposition Decomposition products are hazardous. This material can be decomposed by high temperatures (open flames, glowing metal surfaces, etc.) forming hydrofluoric acid and possibly carbonyl fluoride. These materials are toxic and irritating. avoided. Polymerization Polymerization will not occur. Contact should be

TOXICOLOGICAL INFORMATION
Animal Data ETHANE, 1,1,1,2-TETRAFLUOROEYE: A short duration spray of vapor produced very slight eye irritation. SKIN: Animal testing indicates this material is a slight skin irritant, but not a skin sensitizer. INHALATION: 4 hour, ALC, rat: 567,000 ppm. Single exposure caused: Cardiac sensitization, a potentially fatal disturbance of heart rhythm associated with a heightened sensitivity to the action of epinephrine. Lowest-Observed-Adverse-Effect-Level for cardiac sensitization: 75,000 ppm. Single exposure caused: Lethargy. Narcosis. Increased respiratory rates. These effects were temporary. Single exposure to near lethal doses caused: Pulmonary edema. Repeated exposure caused: Increased adrenals, liver, spleen weight. Decreased uterine, prostate weight. Repeated dosing of higher concentrations caused: the following temporary effects -

56

Application Guide AG 31-007

Tremors.

Incoordination.

CARCINOGENIC, DEVELOPMENTAL, REPRODUCTIVE, MUTAGENIC EFFECTS: In a two-year inhalation study, HFC-134a, at a concentration of 50,000 ppm, produced an increase in late-occurring benign testicular tumors, testicular hyperplasia and testicular weight. The no-effect-level for this study was 10,000 ppm. Animal data show slight fetotoxicity but only at exposure levels producing other toxic effects in the adult animal. Reproductive data on male mice show: No change in reproductive performance. Tests have shown that this material does not cause genetic damage in bacterial or mammalian cell cultures, or in animals. In animal testing, this material has not caused permanent genetic damage in reproductive cells of mammals (has not produced heritable genetic damage).

ECOLOGICAL INFORMATION
Ecotoxicological Information AQUATIC TOXICITY: 48 hour EC50 - Daphnia magna: 980 mg/L. 96 hour LC50 - Rainbow trout: 450 mg/L

DISPOSAL CONSIDERATIONS
Waste Disposal Contaminated HFC-134a can be recovered by distillation or removed to a permitted waste disposal facility. Comply with Federal, State, and local regulations.

TRANSPORTATION INFORMATION
Shipping Information DOT/IMO Proper Shipping Name Hazard Class UN No. DOT/IMO Label Shipping Containers Tank Cars. Tank Trucks. Ton Tanks. Cylinders. : : : : 1,1,1,2-TETRAFLUOROETHANE 2.2 3159 NONFLAMMABLE GAS

Application Guide AG 31-007

57

REGULATORY INFORMATION
U.S. Federal Regulations TSCA Inventory Status : Reported/Included.

TITLE III HAZARD CLASSIFICATIONS SECTIONS 311, 312 Acute Chronic Fire Reactivity Pressure : : : : : Yes Yes No No Yes

HAZARDOUS CHEMICAL LISTS SARA Extremely Hazardous Substance: No CERCLA Hazardous Substance : No SARA Toxic Chemical : No

OTHER INFORMATION
NFPA, NPCA-HMIS NPCA-HMIS Rating Health Flammability Reactivity : 1 : 0 : 1

Personal Protection rating to be supplied by user depending on use conditions. Additional Information MEDICAL USE: CAUTION: Do not use in medical applications involving permanent implantation in the human body. For other medical applications see DuPont CAUTION Bulletin No. H-50102. The data in this Material Safety Data Sheet relates only to the specific material designated herein and does not relate to use in combination with any other material or in any process. Responsibility for MSDS : MSDS Coordinator > : DuPont Fluoroproducts Address : Wilmington, DE 19898 Telephone : (800) 441-7515 # Indicates updated section. End of MSDS

58

Application Guide AG 31-007

Appendix 2 Refrigerant Propertiesa

Table 10 Thermodynamic Properties of 22
Temp Pressure [F]
-150 -145 -140 -135 -130 -125 -120 -115 -110 -105 -100 -95 -90 -85 -80 -75 -70 -65 -60 -55 -50 -45 -41.46 -40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205.06

Density [lb/ft^3] (L)

98.28 97.82 97.36 96.9 96.44 95.98 95.52 95.06 94.59 94.13 93.66 93.19 92.71 92.24 91.76 91.28 90.79 90.31 89.82 89.33 88.83 88.33 98.97 87.82 87.32 86.8 86.29 85.76 85.24 84.71 84.17 83.63 83.08 82.52 81.96 81.39 80.82 80.24 79.65 79.05 78.44 77.83 77.2 76.57 75.92 75.27 74.6 73.92 73.23 72.52 71.8 71.06 70.3 69.52 68.72 67.9 67.05 66.18 65.27 64.32 63.34 62.31 61.22 60.07 58.84 57.53 56.1 54.52 52.74 50.67 48.14 44.68 32.70

Volume [ft^3/lb] (V)

146.1 114.6 90.76 72.49 58.38 47.39 38.75 31.9 26.44 22.06 18.51 15.62 13.26 11.31 9.694 8.349 7.222 6.274 5.473 4.792 4.212 3.715 3.4054 3.287 2.918 2.598 2.32 2.078 1.866 1.679 1.515 1.37 1.242 1.128 1.026 0.9354 0.8543 0.7815 0.7161 0.6572 0.604 0.5558 0.5122 0.4725 0.4364 0.4035 0.3734 0.3459 0.3207 0.2975 0.2762 0.2566 0.2385 0.2217 0.2062 0.1918 0.1785 0.166 0.1544 0.1435 0.1334 0.1238 0.1149 0.1064 0.09836 0.09072 0.0834 0.07635 0.06948 0.06265 0.05565 0.0479 .0.0306

Enthalpy [Btu/R-lb] (L) (V)

-28.12 -26.85 -25.58 -24.31 -23.05 -21.78 -20.51 -19.24 -17.97 -16.7 -15.43 -14.15 -12.88 -11.6 -10.33 -9.046 -7.763 -6.477 -5.189 -3.897 -2.602 -1.303 -0.381 0 1.308 2.62 3.937 5.26 6.588 7.923 9.263 10.61 11.96 13.33 14.69 16.07 17.46 18.85 20.25 21.66 23.08 24.51 25.96 27.41 28.87 30.35 31.84 33.34 34.86 36.39 37.94 39.5 41.08 42.69 44.31 45.95 47.62 49.32 51.04 52.8 54.59 56.42 58.31 60.24 62.24 64.31 66.47 68.76 71.2 73.86 76.88 80.59 91.21 87.57 88.15 88.73 89.31 89.9 90.49 91.07 91.66 92.25 92.84 93.43 94.02 94.61 95.19 95.78 96.36 96.94 97.51 98.09 98.66 99.22 99.79 100.343 100.3 100.9 101.4 102 102.5 103 103.6 104.1 104.6 105.1 105.6 106.1 106.5 107 107.4 107.9 108.3 108.7 109.1 109.5 109.9 110.3 110.6 110.9 111.2 111.5 111.8 112 112.3 112.5 112.7 112.8 112.9 113 113 113 113 112.9 112.8 112.5 112.2 111.9 111.4 110.8 110 109 107.7 105.8 103 91.21

Entropy [Btu/R-lb] (L) (V)

-0.07757 -0.07351 -0.06951 -0.06557 -0.0617 -0.05788 -0.05412 -0.05041 -0.04675 -0.04315 -0.03959 -0.03608 -0.03261 -0.02918 -0.0258 -0.02245 -0.01915 -0.01587 -0.01264 -0.00943 -0.00626 -0.00311 0-.00091 0 0.00309 0.00615 0.00918 0.0122 0.01519 0.01815 0.0211 0.02403 0.02694 0.02983 0.0327 0.03556 0.03841 0.04124 0.04406 0.04686 0.04966 0.05244 0.05522 0.05798 0.06074 0.0635 0.06625 0.06899 0.07173 0.07447 0.07721 0.07996 0.0827 0.08545 0.08821 0.09098 0.09376 0.09656 0.09937 0.1022 0.1051 0.108 0.111 0.114 0.1171 0.1202 0.1235 0.1269 0.1306 0.1345 0.1389 0.1444 0.1601 0.296 0.2919 0.2881 0.2844 0.2809 0.2776 0.2744 0.2714 0.2685 0.2657 0.2631 0.2606 0.2582 0.2559 0.2537 0.2516 0.2495 0.2476 0.2458 0.244 0.2423 0.2407 0.2395 0.2391 0.2376 0.2361 0.2348 0.2334 0.2321 0.2309 0.2296 0.2285 0.2273 0.2263 0.2252 0.2242 0.2231 0.2222 0.2212 0.2203 0.2194 0.2185 0.2176 0.2167 0.2159 0.215 0.2142 0.2133 0.2125 0.2117 0.2108 0.21 0.2091 0.2083 0.2074 0.2065 0.2056 0.2046 0.2036 0.2026 0.2015 0.2004 0.1992 0.1979 0.1965 0.195 0.1933 0.1914 0.1892 0.1865 0.1832 0.1784 0.1601

[psia]
0.2627 0.34 0.4359 0.554 0.6981 0.8725 1.082 1.332 1.629 1.979 2.388 2.865 3.417 4.053 4.782 5.615 6.561 7.631 8.836 10.19 11.7 13.39 14.67 15.26 17.34 19.62 22.14 24.91 27.93 31.23 34.82 38.73 42.96 47.54 52.48 57.79 63.51 69.65 76.22 83.26 90.76 98.76 107.3 116.3 125.9 136.1 146.9 158.3 170.4 183.1 196.5 210.6 225.5 241.1 257.5 274.7 292.7 311.6 331.4 352.1 373.7 396.4 420 444.7 470.6 497.5 525.6 555 585.6 617.6 651.1 686.2 723.7

Specific Heat [Btu/lb-F] (L) (V)

0.2536 0.2536 0.2536 0.2536 0.2536 0.2537 0.2537 0.2538 0.254 0.2541 0.2543 0.2546 0.2549 0.2552 0.2556 0.2561 0.2566 0.2571 0.2577 0.2583 0.2591 0.2598 0.2604 0.2606 0.2615 0.2625 0.2635 0.2645 0.2656 0.2668 0.2681 0.2694 0.2708 0.2722 0.2737 0.2753 0.277 0.2787 0.2806 0.2825 0.2845 0.2866 0.2889 0.2913 0.2938 0.2964 0.2992 0.3022 0.3054 0.3089 0.3126 0.3166 0.3209 0.3257 0.3309 0.3367 0.3431 0.3504 0.3585 0.3679 0.3787 0.3913 0.4063 0.4243 0.4467 0.475 0.5124 0.5641 0.641 0.7681 1.02 1.778 0.1185 0.1194 0.1204 0.1213 0.1223 0.1233 0.1244 0.1254 0.1265 0.1276 0.1288 0.13 0.1312 0.1324 0.1337 0.135 0.1363 0.1377 0.1392 0.1406 0.1422 0.1438 0.1449 0.1454 0.1471 0.1488 0.1506 0.1525 0.1544 0.1564 0.1585 0.1607 0.1629 0.1652 0.1676 0.1702 0.1728 0.1755 0.1783 0.1813 0.1844 0.1877 0.1911 0.1947 0.1985 0.2025 0.2067 0.2112 0.216 0.2212 0.2267 0.2327 0.2391 0.2461 0.2538 0.2623 0.2717 0.2822 0.2941 0.3076 0.3233 0.3416 0.3633 0.3897 0.4225 0.4643 0.5198 0.5972 0.7132 0.9067 1.295 2.472

Sound Spd. [ft/s] (L) (V)

3716 3673 3630 3587 3544 3501 3458 3415 3373 3330 3287 3245 3202 3160 3118 3075 3033 2990 2948 2906 2863 2821 2791 2778 2736 2694 2651 2609 2566 2524 2481 2438 2396 2353 2310 2268 2225 2182 2139 2096 2053 2010 1967 1924 1880 1836 1793 1749 1705 1660 1615 1570 1525 1479 1433 1387 1340 1292 1244 1195 1146 1095 1044 992.3 939 884.3 827.8 768.8 706.5 639.3 565.2 480.1 0.0 469.7 473 476.2 479.3 482.4 485.5 488.5 491.4 494.2 497 499.7 502.4 504.9 507.4 509.8 512.2 514.4 516.5 518.6 520.5 522.4 524.1 525.3 525.8 527.3 528.7 530 531.2 532.3 533.2 534 534.7 535.3 535.7 536 536.1 536.1 535.9 535.6 535.1 534.4 533.6 532.6 531.5 530.1 528.6 526.9 525 522.9 520.6 518.1 515.3 512.4 509.2 505.8 502.1 498.1 493.9 489.4 484.6 479.5 474.1 468.4 462.3 455.8 449 441.6 433.9 425.6 416.6 406.9 395.8 0.0

Viscosity [lbm/ft-h] (L) V)

2.0916 1.98 1.8756 1.7784 1.692 1.6128 1.5372 1.4688 1.404 1.3464 1.2888 1.2384 1.188 1.1448 1.1016 1.0584 1.0224 0.9864 0.9504 0.918 0.8856 0.8568 0.837 0.828 0.8028 0.7776 0.7524 0.7272 0.7056 0.684 0.6624 0.6408 0.6228 0.6048 0.5868 0.5688 0.5508 0.5328 0.5184 0.504 0.4896 0.4716 0.4608 0.4464 0.432 0.4176 0.4068 0.3924 0.3816 0.3708 0.3564 0.3456 0.3348 0.324 0.3132 0.3024 0.2916 0.2808 0.27 0.2592 0.2484 0.2412 0.2304 0.2196 0.2088 0.198 0.1872 0.1764 0.1656 0.1512 0.1368 0.1224 0.017424 0.017712 0.018 0.018288 0.01854 0.018828 0.019116 0.019404 0.019692 0.01998 0.020268 0.020556 0.020844 0.021132 0.02142 0.021672 0.02196 0.022248 0.022536 0.022824 0.023112 0.0234 0.0237 0.023688 0.02394 0.024228 0.024516 0.024804 0.025092 0.02538 0.025668 0.025956 0.026244 0.026532 0.02682 0.027108 0.027396 0.02772 0.028008 0.028296 0.02862 0.028908 0.029232 0.029556 0.02988 0.030204 0.030564 0.030888 0.031248 0.031608 0.032004 0.032364 0.032796 0.033192 0.03366 0.034092 0.034596 0.0351 0.03564 0.036216 0.036864 0.037548 0.038268 0.039096 0.039996 0.04104 0.042192 0.043596 0.045252 0.04734 0.05022 0.05472 -

Therm. Cond. [Btu/h-ft-R] (L) (V)

0.0831 0.08223 0.08137 0.08052 0.07967 0.07883 0.07799 0.07717 0.07635 0.07553 0.07472 0.07392 0.07312 0.07232 0.07153 0.07075 0.06997 0.0692 0.06843 0.06766 0.0669 0.06614 0.0656 0.06539 0.06464 0.06389 0.06315 0.06241 0.06167 0.06093 0.0602 0.05947 0.05874 0.05802 0.05729 0.05657 0.05585 0.05513 0.05441 0.05369 0.05297 0.05225 0.05153 0.05081 0.05009 0.04937 0.04865 0.04793 0.04721 0.04649 0.04576 0.04503 0.0443 0.04357 0.04283 0.04209 0.04135 0.0406 0.03985 0.0391 0.03834 0.03759 0.03683 0.03608 0.03535 0.03464 0.034 0.03347 0.03318 0.03338 0.03474 0.03946 0.00255 0.00261 0.00267 0.00274 0.0028 0.00286 0.00293 0.003 0.00306 0.00313 0.0032 0.00327 0.00334 0.00341 0.00348 0.00355 0.00363 0.0037 0.00378 0.00386 0.00394 0.00402 0.00407 0.0041 0.00418 0.00426 0.00435 0.00444 0.00452 0.00461 0.00471 0.0048 0.00489 0.00499 0.00509 0.00519 0.0053 0.0054 0.00551 0.00562 0.00574 0.00586 0.00598 0.00611 0.00625 0.00638 0.00653 0.00668 0.00684 0.00701 0.00718 0.00737 0.00757 0.00778 0.00801 0.00825 0.00851 0.0088 0.00911 0.00946 0.00984 0.01027 0.01076 0.01131 0.01195 0.0127 0.0136 0.0147 0.01609 0.01793 0.02061 0.02574

NIST Refprop, NIST Standard Reference Database 23 Version 6.01.

59

Application Guide AG 31-007

Table 11 Thermodynamic Properties of 123

Temp [F]
-140 -135 -130 -125 -120 -115 -110 -105 -100 -95 -90 -85 -80 -75 -70 -65 -60 -55 -50 -45 -40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 82.08 85 90 95 100 105 110 115 120 125 130 135 140 145 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 362.63

Pressure [psia]
0.00302 0.00427 0.00598 0.00826 0.01129 0.01526 0.02043 0.02707 0.03556 0.04629 0.05975 0.07651 0.09721 0.1226 0.1536 0.191 0.236 0.2899 0.3539 0.4296 0.5185 0.6226 0.7438 0.8843 1.046 1.232 1.445 1.688 1.963 2.274 2.625 3.019 3.46 3.952 4.499 5.107 5.778 6.519 7.334 8.229 9.208 10.28 11.44 12.71 14.09 14.7 15.58 17.19 18.93 20.8 22.82 24.98 27.3 29.78 32.43 35.25 38.26 41.46 44.87 48.48 56.36 65.17 74.99 85.87 97.89 111.1 125.7 141.6 158.9 177.8 198.3 220.5 244.6 270.5 298.5 328.7 361.2 396.1 433.8 474.4 518.7 531.10

Density [lb/ft^3] (L)

108.9 108.5 108.1 107.7 107.3 107 106.6 106.2 105.8 105.4 105 104.6 104.3 103.9 103.5 103.1 102.7 102.3 101.9 101.5 101.1 100.7 100.3 99.94 99.54 99.14 98.73 98.33 97.92 97.51 97.1 96.69 96.28 95.86 95.44 95.02 94.6 94.17 93.74 93.31 92.88 92.44 92.01 91.56 91.12 90.94 90.67 90.22 89.77 89.31 88.85 88.39 87.92 87.45 86.98 86.5 86.01 85.52 85.03 84.53 83.52 82.49 81.43 80.34 79.23 78.08 76.89 75.66 74.38 73.04 71.64 70.16 68.6 66.92 65.11 63.12 60.91 58.37 55.33 51.32 43.97 34.34

Volume [ft^3/lb] (V)

7432 5331 3871 2843 2112 1585 1201 918.9 709.5 552.5 433.8 343.3 273.8 219.9 177.8 144.7 118.6 97.72 81 67.52 56.58 47.65 40.33 34.3 29.3 25.14 21.66 18.73 16.26 14.17 12.4 10.88 9.578 8.459 7.494 6.659 5.933 5.3 4.747 4.263 3.837 3.462 3.13 2.836 2.575 2.475 2.343 2.136 1.95 1.784 1.635 1.501 1.379 1.27 1.171 1.081 0.9996 0.9253 0.8577 0.7959 0.6876 0.5965 0.5195 0.4539 0.3979 0.3497 0.308 0.2719 0.2404 0.2128 0.1885 0.167 0.1479 0.1309 0.1155 0.1016 0.08887 0.07704 0.06578 0.05444 0.04031 0.0291

Enthalpy [Btu/R-lb] (L)

-22.24 -21.14 -20.03 -18.93 -17.83 -16.72 -15.62 -14.51 -13.41 -12.3 -11.2 -10.09 -8.975 -7.862 -6.746 -5.629 -4.509 -3.386 -2.26 -1.132 0 1.135 2.272 3.414 4.558 5.706 6.857 8.012 9.17 10.33 11.5 12.67 13.84 15.02 16.2 17.38 18.57 19.76 20.96 22.16 23.36 24.57 25.78 27 28.22 28.73 29.44 30.67 31.9 33.14 34.38 35.63 36.88 38.13 39.39 40.66 41.93 43.2 44.48 45.76 48.35 50.95 53.58 56.24 58.92 61.63 64.37 67.14 69.95 72.8 75.7 78.65 81.67 84.75 87.92 91.19 94.59 98.19 102.1 106.5 112.7 118.8

Entropy [Btu/R-lb] (L)

-0.0605 -0.05707 -0.0537 -0.05037 -0.0471 -0.04388 -0.0407 -0.03756 -0.03447 -0.03141 -0.0284 -0.02542 -0.02247 -0.01956 -0.01668 -0.01383 -0.01101 -0.00821 -0.00545 -0.00271 0 0.00269 0.00535 0.00799 0.01061 0.0132 0.01578 0.01833 0.02086 0.02337 0.02587 0.02834 0.0308 0.03324 0.03566 0.03806 0.04045 0.04282 0.04518 0.04752 0.04984 0.05215 0.05444 0.05673 0.05899 0.05993 0.06124 0.06348 0.06571 0.06792 0.07012 0.07231 0.07449 0.07665 0.07881 0.08095 0.08308 0.0852 0.08732 0.08942 0.09359 0.09773 0.1018 0.1059 0.11 0.114 0.118 0.122 0.126 0.13 0.134 0.1379 0.142 0.146 0.1501 0.1543 0.1585 0.163 0.1677 0.173 0.1804 0.1877

Specific Heat [Btu/lb-F] (L)

0.221 0.2208 0.2207 0.2207 0.2206 0.2207 0.2208 0.2209 0.2211 0.2214 0.2217 0.222 0.2224 0.2228 0.2233 0.2238 0.2243 0.2248 0.2254 0.226 0.2266 0.2272 0.2279 0.2285 0.2292 0.2299 0.2306 0.2313 0.232 0.2327 0.2334 0.2341 0.2349 0.2356 0.2364 0.2371 0.2379 0.2387 0.2394 0.2402 0.241 0.2418 0.2426 0.2434 0.2442 0.2445 0.245 0.2458 0.2467 0.2475 0.2484 0.2492 0.2501 0.251 0.252 0.2529 0.2539 0.2548 0.2559 0.2569 0.2591 0.2614 0.2638 0.2665 0.2694 0.2726 0.2761 0.28 0.2845 0.2896 0.2956 0.3026 0.311 0.3215 0.3349 0.3529 0.3785 0.4186 0.4925 0.683 2.507

Sound Spd. [ft/s] (L)

3928 3891 3854 3816 3778 3740 3702 3664 3626 3587 3549 3510 3472 3433 3394 3356 3317 3279 3240 3202 3164 3126 3087 3049 3012 2974 2936 2899 2862 2825 2788 2751 2714 2678 2641 2605 2569 2533 2498 2462 2427 2392 2357 2322 2287 2273 2252 2218 2184 2149 2115 2081 2047 2014 1980 1946 1913 1879 1846 1813 1746 1680 1614 1548 1482 1416 1349 1283 1216 1148 1080 1012 942 871.5 799.6 726.1 650.3 571.4 487.9 396.8 289.8 0.0

Viscosity [lbm/ft-h] (L)

0 0 0 0 0 0 0 0 0 0 5.112 4.68 4.284 3.96 3.672 3.42 3.204 2.988 2.808 2.664 2.52 2.376 2.268 2.088 2.016 1.944 1.872 1.8 1.728 1.656 1.584 1.548 1.476 1.44 1.368 1.332 1.296 1.26 1.224 1.152 1.116 1.08 1.044 1.008 1.008 0.978 0.972 0.936 0.9 0.864 0.864 0.828 0.792 0.756 0.756 0.72 0.72 0.684 0.684 0.648 0.612 0.576 0.54 0.504 0.504 0.468 0.432 0.396 0.396 0.36 0.36 0.324 0.324 0.288 0.288 0.252 0.252 0.216 0.18 0.18 0.144 -

Therm. Cond. [Btu/h-ft-R] (L)

0 0.06687 0.06642 0.06317 0.06275 0.06233 0.06192 0.0615 0.06108 0.06065 0.06022 0.05978 0.05934 0.05888 0.05842 0.05796 0.05749 0.05701 0.05653 0.05604 0.05555 0.05505 0.05455 0.05405 0.05355 0.05305 0.05255 0.05205 0.05155 0.05105 0.05055 0.05005 0.04956 0.04907 0.04858 0.04809 0.04761 0.04714 0.04666 0.04619 0.04573 0.04527 0.04481 0.04436 0.04391 0.0437 0.04347 0.04304 0.0426 0.04217 0.04175 0.04133 0.04092 0.04051 0.04011 0.03971 0.03931 0.03892 0.03853 0.03815 0.03739 0.03665 0.03592 0.0352 0.03449 0.03378 0.03309 0.0324 0.03171 0.03102 0.03032 0.02963 0.02892 0.0282 0.02746 0.02671 0.02593 0.02511 0.02427 0.02343 0.02269

(V)
71.78 72.38 72.97 73.58 74.19 74.8 75.42 76.05 76.68 77.31 77.95 78.59 79.24 79.9 80.56 81.22 81.89 82.56 83.23 83.91 84.59 85.28 85.97 86.66 87.35 88.05 88.75 89.46 90.16 90.87 91.58 92.29 93.01 93.72 94.44 95.16 95.88 96.6 97.32 98.04 98.76 99.48 100.2 100.9 101.6 101.9 102.4 103.1 103.8 104.5 105.2 106 106.7 107.4 108.1 108.8 109.5 110.2 110.9 111.6 113 114.3 115.7 117 118.3 119.6 120.8 122 123.2 124.3 125.4 126.4 127.3 128.1 128.9 129.4 129.8 130 129.7 128.6 125.1 118.8

(V)
0.2336 0.231 0.2284 0.226 0.2238 0.2217 0.2197 0.2178 0.216 0.2143 0.2128 0.2113 0.2099 0.2086 0.2074 0.2062 0.2052 0.2042 0.2032 0.2024 0.2016 0.2008 0.2001 0.1995 0.1989 0.1984 0.1979 0.1975 0.1971 0.1967 0.1964 0.1961 0.1958 0.1956 0.1954 0.1953 0.1952 0.1951 0.195 0.195 0.1949 0.1949 0.1949 0.195 0.195 0.195 0.1951 0.1952 0.1953 0.1955 0.1956 0.1958 0.1959 0.1961 0.1963 0.1965 0.1967 0.1969 0.1972 0.1974 0.1979 0.1984 0.1989 0.1995 0.2 0.2005 0.2011 0.2016 0.2021 0.2025 0.203 0.2033 0.2036 0.2039 0.204 0.2039 0.2037 0.2032 0.2022 0.2004 0.1955 0.1877

(V)
0.1181 0.1192 0.1203 0.1215 0.1226 0.1237 0.1248 0.1259 0.127 0.1281 0.1291 0.1302 0.1313 0.1324 0.1334 0.1345 0.1356 0.1366 0.1377 0.1388 0.1398 0.1409 0.142 0.143 0.1441 0.1452 0.1463 0.1473 0.1484 0.1495 0.1506 0.1517 0.1528 0.154 0.1551 0.1562 0.1574 0.1585 0.1597 0.1609 0.1621 0.1633 0.1645 0.1657 0.1669 0.1951 0.1682 0.1695 0.1707 0.172 0.1734 0.1747 0.1761 0.1775 0.1789 0.1803 0.1818 0.1833 0.1848 0.1863 0.1896 0.1929 0.1965 0.2004 0.2045 0.2089 0.2138 0.2191 0.2251 0.2319 0.2398 0.249 0.2603 0.2742 0.2922 0.3166 0.352 0.4084 0.5138 0.7861 3.263

(V)
341.7 344.2 346.6 349 351.4 353.8 356.2 358.5 360.8 363.1 365.4 367.6 369.9 372.1 374.3 376.4 378.5 380.7 382.7 384.8 386.8 388.8 390.7 392.7 394.5 396.4 398.2 399.9 401.7 403.3 405 406.6 408.1 409.6 411 412.4 413.7 414.9 416.1 417.3 418.3 419.4 420.3 421.2 422 422.3 422.7 423.3 423.9 424.4 424.8 425.2 425.4 425.6 425.6 425.6 425.5 425.3 425 424.6 423.5 422 420.1 417.7 414.7 411.3 407.3 402.8 397.6 391.7 385.1 377.7 369.4 360.2 349.9 338.5 325.7 311.5 295.4 277 255.2 0.0

V)
0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.01690 0.01714 0.01739 0.01763 0.01788 0.01812 0.01837 0.01862 0.01886 0.01911 0.01935 0.01960 0.01984 0.02009 0.02033 0.02058 0.02089 0.02115 0.02141 0.02167 0.02193 0.02218 0.02244 0.02269 0.02295 0.02320 0.02345 0.02370 0.02395 0.02420 0.02444 0.02469 0.02493 0.02517 0.02541 0.02565 0.02588 0.02612 0.0262 0.02636 0.02659 0.02682 0.02705 0.02728 0.02751 0.02775 0.02797 0.02820 0.02843 0.02866 0.02888 0.02911 0.02934 0.02980 0.03026 0.03073 0.03122 0.03171 0.03223 0.03279 0.03338 0.03401 0.03471 0.03549 0.03638 0.03740 0.03859 0.04002 0.04179 0.04401 0.04694 0.05104 0.05754 0.07301 -

(V)
0 0.00425 0.00435 0.00162 0.00171 0.00181 0.0019 0.00199 0.00208 0.00217 0.00226 0.00235 0.00244 0.00254 0.00263 0.00272 0.00281 0.0029 0.00299 0.00308 0.00317 0.00326 0.00335 0.00344 0.00353 0.00362 0.00371 0.00381 0.0039 0.00399 0.00408 0.00417 0.00426 0.00435 0.00444 0.00453 0.00462 0.00471 0.00481 0.0049 0.00499 0.00508 0.00518 0.00527 0.00537 0.00540 0.00546 0.00556 0.00565 0.00575 0.00585 0.00595 0.00604 0.00614 0.00625 0.00635 0.00645 0.00656 0.00666 0.00677 0.00699 0.00722 0.00745 0.00769 0.00795 0.00821 0.00849 0.00877 0.00908 0.0094 0.00974 0.0101 0.0105 0.01092 0.01139 0.01191 0.01251 0.01321 0.01411 0.01539 0.01819

60

Application Guide AG 31-007

Table 12 Thermodynamic Properties of 134a

Temp Pressure Density Volume [F]
-153.5 -150 -145 -140 -135 -130 -125 -120 -115 -110 -105 -100 -95 -90 -85 -80 -75 -70 -65 -60 -55 -50 -45 -40 -35 -30 -25 -20 -15 -14.9 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 213.9

Enthalpy [Btu/R-lb] (L) (V)

-32.99 -31.88 -30.46 -29.05 -27.63 -26.21 -24.79 -23.36 -21.93 -20.5 -19.07 -17.63 -16.18 -14.74 -13.28 -11.83 -10.37 -8.903 -7.432 -5.957 -4.476 -2.989 -1.498 0 1.503 3.013 4.529 6.051 7.58 7.600 9.115 10.66 12.21 13.76 15.33 16.9 18.48 20.07 21.67 23.27 24.89 26.51 28.15 29.8 31.45 33.12 34.8 36.49 38.2 39.91 41.65 43.39 45.15 46.93 48.73 50.55 52.38 54.24 56.12 58.02 59.95 61.92 63.91 65.94 68 70.12 72.28 74.51 76.81 79.19 81.69 84.34 87.21 90.45 94.53 103.89 80.36 80.91 81.6 82.3 83.01 83.73 84.44 85.17 85.9 86.63 87.37 88.11 88.85 89.6 90.35 91.1 91.86 92.61 93.37 94.13 94.89 95.65 96.41 97.17 97.92 98.68 99.43 100.2 100.9 101.0 101.7 102.4 103.2 103.9 104.6 105.3 106.1 106.8 107.5 108.2 108.9 109.5 110.2 110.9 111.5 112.2 112.8 113.4 114 114.6 115.2 115.7 116.3 116.8 117.3 117.8 118.3 118.7 119.1 119.5 119.8 120.1 120.4 120.6 120.7 120.8 120.8 120.8 120.6 120.3 119.8 119.1 118.1 116.5 113.7 103.89

Entropy [Btu/R-lb] (L) (V)

-0.09154 -0.08791 -0.08338 -0.07891 -0.07451 -0.07017 -0.06589 -0.06166 -0.05749 -0.05337 -0.04929 -0.04527 -0.04128 -0.03734 -0.03344 -0.02959 -0.02577 -0.02198 -0.01824 -0.01452 -0.01085 -0.0072 -0.00358 0 0.00356 0.00708 0.01058 0.01406 0.01751 0.01755 0.02093 0.02433 0.02771 0.03107 0.0344 0.03772 0.04101 0.04429 0.04755 0.05079 0.05402 0.05724 0.06044 0.06362 0.0668 0.06996 0.07311 0.07626 0.07939 0.08252 0.08565 0.08877 0.09188 0.095 0.09811 0.1012 0.1044 0.1075 0.1106 0.1138 0.1169 0.1201 0.1233 0.1265 0.1298 0.1331 0.1364 0.1399 0.1433 0.1469 0.1507 0.1546 0.1588 0.1635 0.1694 0.1832 .2793 0.2763 0.2728 0.2694 0.2663 0.2633 0.2605 0.2578 0.2554 0.253 0.2508 0.2487 0.2467 0.2449 0.2432 0.2415 0.24 0.2385 0.2372 0.2359 0.2347 0.2336 0.2325 0.2315 0.2306 0.2297 0.2289 0.2282 0.2274 0.2273 0.2268 0.2262 0.2256 0.225 0.2245 0.224 0.2236 0.2232 0.2228 0.2224 0.2221 0.2217 0.2214 0.2212 0.2209 0.2206 0.2204 0.2201 0.2199 0.2197 0.2194 0.2192 0.219 0.2187 0.2185 0.2183 0.218 0.2177 0.2174 0.2171 0.2167 0.2163 0.2159 0.2154 0.2149 0.2143 0.2136 0.2127 0.2118 0.2107 0.2094 0.2077 0.2056 0.2028 0.1981 0.1832

[psia]
0.057 0.072 0.0968 0.1288 0.1696 0.221 0.2854 0.3653 0.4635 0.5833 0.7284 0.903 1.111 1.359 1.651 1.993 2.392 2.854 3.389 4.002 4.703 5.501 6.406 7.427 8.576 9.862 11.3 12.9 14.67 14.69 16.63 18.79 21.17 23.78 26.63 29.74 33.12 36.8 40.78 45.09 49.74 54.75 60.13 65.91 72.11 78.73 85.8 93.35 101.4 109.9 119 128.6 138.9 149.7 161.1 173.1 185.9 199.3 213.4 228.3 243.9 260.4 277.6 295.7 314.7 334.7 355.5 377.4 400.3 424.4 449.5 475.9 503.6 532.7 563.4 588.7

[lb/ft^3] [ft^3/lb] (L) (V)

99.34 98.97 98.51 98.05 97.59 97.13 96.66 96.2 95.73 95.27 94.8 94.33 93.85 93.38 92.9 92.42 91.94 91.46 90.97 90.49 90 89.5 89 88.5 88 87.49 86.98 86.47 85.95 85.94 85.43 84.9 84.37 83.83 83.29 82.74 82.19 81.63 81.06 80.49 79.9 79.32 78.72 78.11 77.5 76.87 76.24 75.59 74.94 74.27 73.58 72.88 72.17 71.44 70.69 69.93 69.14 68.32 67.49 66.62 65.73 64.8 63.83 62.82 61.76 60.65 59.47 58.21 56.86 55.38 53.76 51.91 49.76 47.08 43.2 31.96 564.85 452.1 341.4 260.6 201 156.5 123 97.48 77.91 62.76 50.94 41.64 34.27 28.38 23.65 19.83 16.71 14.16 12.06 10.32 8.873 7.662 6.644 5.784 5.054 4.433 3.901 3.445 3.051 3.047 2.711 2.415 2.158 1.933 1.736 1.562 1.409 1.274 1.154 1.048 0.9528 0.868 0.792 0.7238 0.6625 0.6072 0.5572 0.512 0.471 0.4338 0.3999 0.369 0.3407 0.3148 0.2911 0.2693 0.2493 0.2308 0.2137 0.198 0.1833 0.1697 0.1571 0.1453 0.1343 0.1239 0.1142 0.1051 0.09637 0.08808 0.08011 0.07236 0.06466 0.05673 0.04769 0.0313

Specific Heat [Btu/lb-F] (L) (V)

0.283 0.283 0.2832 0.2834 0.2838 0.2842 0.2847 0.2853 0.2859 0.2866 0.2874 0.2881 0.2889 0.2898 0.2907 0.2916 0.2925 0.2935 0.2945 0.2955 0.2965 0.2976 0.2987 0.2999 0.301 0.3022 0.3035 0.3047 0.306 0.3061 0.3074 0.3088 0.3102 0.3117 0.3132 0.3147 0.3164 0.3181 0.3198 0.3216 0.3235 0.3255 0.3275 0.3297 0.3319 0.3343 0.3368 0.3394 0.3422 0.3451 0.3482 0.3515 0.3551 0.3589 0.363 0.3675 0.3723 0.3775 0.3833 0.3897 0.3968 0.4048 0.4138 0.4242 0.4362 0.4504 0.4675 0.4887 0.5156 0.5512 0.6012 0.6768 0.8062 1.083 2.113 0.1399 0.1411 0.1427 0.1443 0.1459 0.1475 0.1491 0.1508 0.1524 0.154 0.1557 0.1573 0.159 0.1607 0.1624 0.1641 0.1658 0.1676 0.1694 0.1713 0.1731 0.1751 0.177 0.179 0.1811 0.1832 0.1853 0.1875 0.1898 0.1898 0.1921 0.1945 0.1969 0.1995 0.2021 0.2047 0.2075 0.2103 0.2132 0.2163 0.2194 0.2226 0.226 0.2294 0.2331 0.2368 0.2408 0.2449 0.2492 0.2537 0.2585 0.2636 0.269 0.2747 0.2809 0.2875 0.2948 0.3026 0.3112 0.3208 0.3315 0.3435 0.3571 0.3729 0.3914 0.4134 0.44 0.4733 0.5159 0.5729 0.6532 0.7751 0.9835 1.425 3.008

Sound Spd. [ft/s] (L) (V)

3723 3638 3592 3545 3499 3452 3406 3360 3314 3269 3223 3178 3132 3087 3043 2998 2954 2909 2866 2822 2778 2735 2691 2648 2605 2563 2520 2477 2435 2434 2393 2350 2308 2266 2224 2182 2140 2098 2056 2014 1973 1931 1889 1847 1805 1763 1721 1679 1636 1594 1551 1509 1466 1423 1380 1337 1294 1250 1206 1162 1117 1072 1027 980.4 933.5 885.7 836.8 786.5 734.5 680.5 624.1 564.9 502.5 436 363.4 0 416 418.3 421.3 424.2 427.1 429.9 432.7 435.4 438.2 440.8 443.4 446 448.5 450.9 453.3 455.6 457.8 460 462.1 464.1 466 467.8 469.6 471.2 472.8 474.2 475.6 476.8 477.9 477.9 478.9 479.8 480.5 481.1 481.6 482 482.2 482.2 482.2 481.9 481.5 481 480.3 479.4 478.3 477 475.6 474 472.2 470.1 467.9 465.4 462.7 459.8 456.7 453.2 449.6 445.6 441.3 436.8 432 426.8 421.2 415.3 409.1 402.4 395.3 387.7 379.6 371 361.8 352 341.3 329.4 315.5 0

Viscosity [lbm/ft-h] (L) V)

5.262 4.7916 4.2912 3.8808 3.5352 3.24 2.9844 2.7612 2.5668 2.394 2.2428 2.106 1.98 1.8684 1.7676 1.674 1.5876 1.5084 1.4364 1.368 1.3068 1.2492 1.1916 1.1412 1.0944 1.0512 1.008 0.9684 0.9288 0.928 0.8928 0.8604 0.828 0.7992 0.7704 0.7416 0.7164 0.6876 0.666 0.6408 0.6192 0.5976 0.576 0.558 0.54 0.522 0.504 0.486 0.468 0.4536 0.4356 0.4212 0.4068 0.3924 0.378 0.3636 0.3528 0.3384 0.324 0.3132 0.2988 0.288 0.2772 0.2628 0.252 0.2412 0.2304 0.216 0.2052 0.1944 0.18 0.1692 0.1548 0.1404 0.120 0.0156 0.01584 0.016128 0.016452 0.01674 0.017028 0.017316 0.017604 0.017892 0.01818 0.018468 0.01872 0.019008 0.019296 0.019584 0.019872 0.02016 0.020412 0.0207 0.020988 0.02124 0.021528 0.02178 0.022068 0.022356 0.022608 0.022896 0.023148 0.023436 0.0234 0.023688 0.02394 0.024228 0.02448 0.024768 0.02502 0.025308 0.02556 0.025848 0.026136 0.026388 0.026676 0.026964 0.027252 0.02754 0.027828 0.028116 0.02844 0.028764 0.029052 0.029376 0.029736 0.03006 0.03042 0.03078 0.031176 0.031572 0.031968 0.032436 0.032868 0.033372 0.033876 0.034452 0.035064 0.035712 0.036432 0.037224 0.038124 0.039132 0.04032 0.041724 0.043452 0.04572 0.048852 0.0543

Therm. Cond. [Btu/h-ft-R] (L) (V)

0.084 0.0832 0.08223 0.08126 0.08031 0.07936 0.07843 0.07751 0.0766 0.0757 0.0748 0.07392 0.07304 0.07217 0.07132 0.07047 0.06962 0.06879 0.06796 0.06714 0.06633 0.06553 0.06473 0.06394 0.06316 0.06238 0.06161 0.06084 0.06009 0.06010 0.05933 0.05858 0.05784 0.0571 0.05637 0.05564 0.05492 0.0542 0.05348 0.05277 0.05206 0.05136 0.05066 0.04996 0.04926 0.04857 0.04787 0.04718 0.04649 0.04581 0.04512 0.04443 0.04374 0.04306 0.04237 0.04168 0.04099 0.0403 0.03961 0.03891 0.03821 0.03751 0.0368 0.03609 0.03537 0.03465 0.03392 0.0332 0.03247 0.03175 0.03106 0.03044 0.02997 0.02996 0.0316 0.00178 0.00188 0.00201 0.00214 0.00227 0.0024 0.00253 0.00265 0.00278 0.00291 0.00304 0.00317 0.0033 0.00343 0.00356 0.00369 0.00382 0.00395 0.00408 0.0042 0.00433 0.00446 0.0046 0.00473 0.00486 0.00499 0.00512 0.00525 0.00538 0.00486 0.00552 0.00565 0.00578 0.00592 0.00605 0.00619 0.00632 0.00646 0.0066 0.00674 0.00688 0.00703 0.00717 0.00732 0.00747 0.00762 0.00777 0.00793 0.00809 0.00825 0.00842 0.0086 0.00878 0.00897 0.00916 0.00936 0.00958 0.00981 0.01005 0.01031 0.01058 0.01089 0.01122 0.01158 0.01199 0.01245 0.01297 0.01358 0.0143 0.01516 0.01623 0.0176 0.01949 0.0224 0.02848

Application Guide AG 31-007

61

Table 13 Thermodynamic Properties of 407a

Press. [psia] (b)
1 2 3 4 5 6 7 8 10 12 14 14.7 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 55 60 65 70 75 80 85 90 95 100 110 120 130 140 150 160 170 180 190 200 220 240 260 280 300 320 340 360 380 400 450 500 550 600 650 672.20 -125.9 -109 -98.15 -89.97 -83.32 -77.68 -72.75 -68.37 -60.78 -54.32 -48.67 -46.82 -43.63 -39.06 -34.88 -31.02 -27.42 -24.05 -20.87 -17.87 -15.02 -12.3 -9.708 -7.222 -4.835 -2.539 -0.325 1.813 3.881 5.884 10.63 15.07 19.23 23.15 26.86 30.39 33.76 36.98 40.07 43.04 48.66 53.91 58.84 63.49 67.91 72.1 76.11 79.94 83.62 87.16 93.86 100.1 106 111.6 116.8 121.9 126.6 131.2 135.6 139.9 149.8 158.9 167.4 175.3 182.8 186.9

Temp. F (d)
-111.6 -95 -84.37 -76.35 -69.83 -64.3 -59.47 -55.18 -47.74 -41.41 -35.88 -34.08 -30.94 -26.47 -22.37 -18.59 -15.06 -11.76 -8.654 -5.715 -2.925 -0.267 2.271 4.703 7.037 9.283 11.45 13.54 15.56 17.52 22.16 26.48 30.54 34.37 38 41.44 44.72 47.86 50.87 53.76 59.23 64.33 69.12 73.64 77.91 81.98 85.86 89.57 93.12 96.54 103 109 114.7 120 125 129.8 134.4 138.7 142.9 146.8 156.1 164.6 172.3 179.2 185.4 186.9

Density [lb/ft^3] (L)

94.25 92.61 91.54 90.72 90.06 89.48 88.98 88.53 87.74 87.07 86.47 86.28 85.93 85.44 84.99 84.57 84.18 83.81 83.45 83.12 82.8 82.49 82.2 81.91 81.64 81.37 81.12 80.87 80.63 80.39 79.83 79.3 78.79 78.31 77.85 77.41 76.98 76.57 76.17 75.78 75.03 74.33 73.65 72.99 72.36 71.75 71.16 70.58 70.01 69.46 68.38 67.33 66.31 65.3 64.32 63.34 62.36 61.39 60.41 59.43 56.9 54.21 51.22 47.62 42.52 31.6

Volume [ft^3/lb] (V)

43.06 22.47 15.36 11.73 9.519 8.023 6.944 6.126 4.968 4.186 3.621 3.459 3.193 2.857 2.586 2.363 2.176 2.017 1.88 1.76 1.655 1.562 1.479 1.405 1.337 1.276 1.22 1.169 1.122 1.079 0.9835 0.9038 0.8359 0.7773 0.7264 0.6815 0.6418 0.6063 0.5745 0.5457 0.4957 0.4538 0.4181 0.3873 0.3605 0.337 0.316 0.2974 0.2806 0.2654 0.239 0.2169 0.198 0.1817 0.1674 0.1548 0.1436 0.1336 0.1245 0.1162 0.09841 0.08359 0.07075 0.05896 0.04651 0.0317

Enthalpy [Btu/R-lb] (L) (V)

-26.02 -21.01 -17.76 -15.31 -13.3 -11.59 -10.09 -8.755 -6.431 -4.443 -2.696 -2.12 -1.131 0.292 1.6 2.814 3.947 5.012 6.018 6.973 7.882 8.75 9.582 10.38 11.15 11.89 12.61 13.3 13.97 14.63 16.18 17.64 19.02 20.32 21.56 22.75 23.88 24.98 26.03 27.04 28.98 30.8 32.53 34.17 35.74 37.25 38.7 40.1 41.45 42.76 45.28 47.66 49.95 52.14 54.25 56.3 58.29 60.23 62.13 64 68.56 73.07 77.66 82.58 88.57 98.5 93.37 95.79 97.35 98.52 99.47 100.3 101 101.6 102.6 103.5 104.3 104.5 105 105.6 106.2 106.7 107.2 107.6 108 108.4 108.8 109.1 109.5 109.8 110.1 110.4 110.6 110.9 111.2 111.4 112 112.5 113 113.4 113.8 114.2 114.6 114.9 115.2 115.5 116.1 116.6 117 117.5 117.8 118.2 118.5 118.7 119 119.2 119.6 119.9 120.2 120.3 120.4 120.5 120.5 120.4 120.3 120.1 119.4 118.3 116.7 114.1 109.5 98.5

Entropy [Btu/R-lb] (L) (V)

-0.06921 -0.05456 -0.04546 -0.03874 -0.03337 -0.02887 -0.02498 -0.02155 -0.01567 -0.01074 -0.00647 -0.00508 -0.0027 0.00069 0.00378 0.00661 0.00923 0.01168 0.01397 0.01613 0.01817 0.0201 0.02195 0.02371 0.02539 0.02701 0.02856 0.03006 0.03151 0.0329 0.0362 0.03926 0.04212 0.04481 0.04735 0.04975 0.05204 0.05422 0.05631 0.05831 0.06209 0.06561 0.0689 0.07201 0.07495 0.07775 0.08042 0.08297 0.08542 0.08778 0.09225 0.09644 0.1004 0.1041 0.1077 0.1112 0.1145 0.1177 0.1208 0.1238 0.1311 0.1382 0.1452 0.1527 0.1618 0.1771 0.2813 0.2722 0.2672 0.2638 0.2612 0.2591 0.2574 0.2559 0.2535 0.2516 0.25 0.2516 0.2487 0.2475 0.2465 0.2456 0.2448 0.244 0.2434 0.2427 0.2421 0.2416 0.2411 0.2406 0.2402 0.2398 0.2394 0.239 0.2386 0.2383 0.2375 0.2367 0.2361 0.2354 0.2349 0.2344 0.2339 0.2334 0.2329 0.2325 0.2317 0.231 0.2303 0.2297 0.2291 0.2285 0.228 0.2274 0.2269 0.2264 0.2254 0.2245 0.2236 0.2226 0.2217 0.2208 0.2199 0.2189 0.2179 0.2169 0.2141 0.211 0.2072 0.2023 0.1943 0.1771

Specific Heat [ft/s] (L) (V)

0.2948 0.2978 0.2996 0.3011 0.3023 0.3033 0.3043 0.3052 0.3068 0.3082 0.3092 0.3095 0.3107 0.3118 0.3129 0.314 0.3149 0.3159 0.3168 0.3177 0.3186 0.3194 0.3203 0.3211 0.3219 0.3227 0.3234 0.3242 0.3249 0.3257 0.3275 0.3292 0.331 0.3326 0.3343 0.336 0.3376 0.3392 0.3408 0.3424 0.3455 0.3487 0.3518 0.355 0.3582 0.3614 0.3646 0.368 0.3713 0.3748 0.3819 0.3894 0.3974 0.4058 0.415 0.4249 0.4357 0.4476 0.4608 0.4757 0.5228 0.5937 0.7154 0.981 1.988 0.1567 0.1621 0.1659 0.1688 0.1714 0.1736 0.1756 0.1774 0.1807 0.1836 0.1862 0.1875 0.1886 0.1909 0.193 0.195 0.1969 0.1987 0.2004 0.2021 0.2037 0.2053 0.2068 0.2083 0.2098 0.2112 0.2125 0.2139 0.2152 0.2165 0.2197 0.2227 0.2257 0.2285 0.2313 0.2341 0.2368 0.2394 0.242 0.2446 0.2497 0.2547 0.2597 0.2647 0.2697 0.2747 0.2797 0.2848 0.29 0.2953 0.3062 0.3177 0.3299 0.3429 0.357 0.3722 0.3889 0.4074 0.4281 0.4513 0.5252 0.6365 0.8259 1.226 2.655 -

Sound Spd. [Btu/lb-F] (L) (V)

3380 3214 3111 3035 2973 2922 2877 2838 2770 2712 2662 2635 2617 2577 2540 2505 2474 2444 2416 2389 2364 2340 2317 2295 2274 2254 2235 2216 2197 2180 2138 2099 2062 2027 1994 1962 1932 1904 1876 1850 1799 1752 1707 1665 1625 1587 1550 1515 1481 1448 1385 1327 1271 1217 1166 1117 1069 1023 977.9 933.7 826.5 722.1 619.1 516 412.5 484.1 493.2 498.5 502.3 505.2 507.5 509.4 511 513.7 515.7 517.3 517.8 518.6 519.7 520.6 521.3 521.9 522.4 522.9 523.2 523.5 523.7 523.9 524 524.1 524.1 524.2 524.1 524.1 524 523.8 523.4 522.9 522.3 521.6 520.9 520.2 519.4 518.5 517.6 515.7 513.8 511.7 509.5 507.3 505 502.7 500.3 497.9 495.5 490.5 485.4 480.3 475 469.7 464.3 458.8 453.3 447.8 442.1 427.8 413.1 397.9 381.7 362.9 -

Viscosity [lbm/ft-h] (L) (V)

1.944 1.584 1.404 1.296 1.224 1.152 1.116 1.08 1.008 0.936 0.9 0.898 0.864 0.828 0.828 0.792 0.756 0.756 0.72 0.72 0.72 0.684 0.684 0.648 0.648 0.648 0.648 0.612 0.612 0.612 0.576 0.576 0.54 0.54 0.54 0.504 0.504 0.504 0.468 0.468 0.468 0.432 0.432 0.396 0.396 0.396 0.36 0.36 0.36 0.36 0.324 0.324 0.288 0.288 0.288 0.252 0.252 0.252 0.216 0.216 0.216 0.18 0.144 0.144 0.108 0.019368 0.020304 0.020916 0.021348 0.021708 0.022032 0.022284 0.022536 0.022968 0.023328 0.023616 0.0237 0.023904 0.024156 0.024372 0.024588 0.024768 0.024984 0.025164 0.025344 0.025524 0.025668 0.025812 0.025956 0.0261 0.026244 0.026388 0.026496 0.026604 0.026748 0.027036 0.027288 0.02754 0.027792 0.028008 0.028224 0.02844 0.028656 0.028836 0.029052 0.029412 0.029772 0.030096 0.030456 0.03078 0.031068 0.031392 0.03168 0.032004 0.032292 0.032868 0.033444 0.03402 0.034596 0.035172 0.035784 0.03636 0.037008 0.037656 0.03834 0.040176 0.042372 0.04518 0.04914 0.056448 -

Therm. Cond. [Btu/h-ft-R] (L) (V)

0.0866 0.08329 0.08122 0.07968 0.07844 0.07739 0.07649 0.07569 0.07432 0.07316 0.07215 0.0718 0.07126 0.07046 0.06972 0.06905 0.06842 0.06784 0.06729 0.06677 0.06628 0.06581 0.06537 0.06494 0.06453 0.06414 0.06377 0.0634 0.06305 0.06271 0.06191 0.06116 0.06046 0.0598 0.05917 0.05858 0.05802 0.05748 0.05696 0.05646 0.05552 0.05464 0.05382 0.05303 0.05229 0.05159 0.05091 0.05026 0.04964 0.04903 0.04789 0.04681 0.04579 0.04482 0.04389 0.043 0.04214 0.04131 0.04051 0.03973 0.03789 0.0362 0.03474 0.03385 0.03557 0.0034 0.00372 0.00393 0.00409 0.00422 0.00433 0.00443 0.00452 0.00467 0.0048 0.00492 0.00496 0.00503 0.00512 0.00521 0.00529 0.00537 0.00544 0.00551 0.00558 0.00565 0.00571 0.00577 0.00582 0.00588 0.00593 0.00599 0.00604 0.00609 0.00613 0.00625 0.00636 0.00647 0.00657 0.00666 0.00676 0.00685 0.00694 0.00703 0.00711 0.00728 0.00744 0.0076 0.00776 0.00792 0.00807 0.00823 0.00839 0.00854 0.0087 0.00903 0.00936 0.00971 0.01008 0.01046 0.01088 0.01132 0.01179 0.0123 0.01286 0.01448 0.01657 0.01945 0.02397 0.03352 -

62

Application Guide AG 31-007

Table 14 Thermodynamic Properties of 410A

Press. [psia] (b)
1 2 3 4 5 6 7 8 10 12 14 14.70 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 55 60 65 70 75 80 85 90 95 100 110 120 130 140 150 160 170 180 190 200 220 240 260 280 300 320 340 360 380 400 450 500 550 600 650 694.87 -135.8 -119.7 -109.4 -101.7 -95.37 -90.03 -85.37 -81.21 -74.03 -67.93 -62.59 -60.93 -57.82 -53.51 -49.56 -45.91 -42.52 -39.33 -36.34 -33.51 -30.82 -28.26 -25.81 -23.47 -21.22 -19.06 -16.97 -14.96 -13.01 -11.13 -6.654 -2.485 1.426 5.113 8.603 11.92 15.08 18.11 21.01 23.79 29.06 33.98 38.6 42.95 47.08 51 54.74 58.32 61.76 65.06 71.3 77.13 82.6 87.77 92.66 97.31 101.7 106 110 113.9 123.1 131.4 139.1 146.3 152.9 158.4

Temp. F (d)
-135.7 -119.6 -109.4 -101.6 -95.3 -89.95 -85.29 -81.14 -73.96 -67.85 -62.5 -60.74 -57.74 -53.42 -49.47 -45.82 -42.42 -39.23 -36.24 -33.4 -30.71 -28.15 -25.7 -23.35 -21.1 -18.94 -16.85 -14.83 -12.89 -11 -6.523 -2.35 1.564 5.255 8.749 12.07 15.24 18.26 21.17 23.95 29.23 34.15 38.77 43.13 47.26 51.19 54.93 58.52 61.95 65.26 71.5 77.34 82.81 87.97 92.87 97.51 101.9 106.2 110.2 114.1 123.3 131.6 139.3 146.4 153 158.4

Density [lb/ft^3] (L)

92.04 90.46 89.43 88.64 87.99 87.44 86.95 86.52 85.76 85.1 84.52 84.33 84 83.53 83.09 82.69 82.3 81.95 81.61 81.28 80.97 80.68 80.39 80.12 79.85 79.6 79.35 79.11 78.88 78.65 78.11 77.6 77.11 76.65 76.21 75.78 75.37 74.98 74.59 74.22 73.51 72.83 72.19 71.56 70.96 70.38 69.82 69.27 68.74 68.21 67.2 66.21 65.25 64.32 63.4 62.49 61.59 60.69 59.8 58.9 56.63 54.25 51.69 48.79 45.17 34.2

Volume [ft^3/lb] (V)

47.55 24.84 17 12.99 10.54 8.889 7.695 6.79 5.509 4.643 4.017 3.838 3.543 3.171 2.871 2.623 2.416 2.24 2.088 1.955 1.839 1.736 1.643 1.561 1.486 1.418 1.356 1.299 1.247 1.199 1.094 1.005 0.9298 0.8648 0.8083 0.7585 0.7144 0.6751 0.6397 0.6078 0.5523 0.5057 0.4661 0.432 0.4022 0.376 0.3528 0.3321 0.3134 0.2966 0.2673 0.2428 0.2218 0.2037 0.1879 0.174 0.1616 0.1505 0.1405 0.1314 0.1119 0.09571 0.08191 0.06958 0.05773 0.0293

Enthalpy [Btu/R-lb] (L)

-30.47 -25.48 -22.26 -19.82 -17.83 -16.14 -14.66 -13.33 -11.04 -9.079 -7.358 -6.77 -5.817 -4.417 -3.131 -1.939 -0.8265 0.2188 1.206 2.141 3.032 3.882 4.697 5.479 6.231 6.956 7.657 8.335 8.993 9.631 11.15 12.57 13.91 15.19 16.4 17.55 18.66 19.72 20.75 21.73 23.61 25.39 27.06 28.66 30.18 31.64 33.05 34.4 35.71 36.98 39.41 41.72 43.92 46.04 48.07 50.05 51.96 53.83 55.65 57.44 61.79 66.06 70.33 74.77 79.71 90.2

Entropy [Btu/R-lb] (L)

-0.08217 -0.06715 -0.05782 -0.05093 -0.04543 -0.04082 -0.03685 -0.03334 -0.02734 -0.02231 -0.01796 -0.0165 -0.01411 -0.01066 -0.00752 -0.00463 -0.00197 0.00052 0.00285 0.00504 0.00711 0.00908 0.01095 0.01274 0.01445 0.01609 0.01766 0.01918 0.02065 0.02206 0.0254 0.0285 0.0314 0.03412 0.03669 0.03912 0.04143 0.04364 0.04575 0.04778 0.05159 0.05515 0.05848 0.06161 0.06458 0.0674 0.07009 0.07267 0.07514 0.07751 0.08201 0.08623 0.09021 0.09398 0.09758 0.101 0.1043 0.1075 0.1107 0.1137 0.1209 0.1279 0.1348 0.1419 0.1496 0.1663

Specific Heat [ft/s] (L)

0.309 0.3122 0.3139 0.3152 0.3162 0.3171 0.3179 0.3187 0.3201 0.3213 0.3225 0.3221 0.3236 0.3246 0.3256 0.3266 0.3275 0.3284 0.3293 0.3301 0.331 0.3318 0.3326 0.3334 0.3342 0.335 0.3357 0.3365 0.3372 0.338 0.3398 0.3416 0.3433 0.345 0.3467 0.3484 0.3501 0.3517 0.3534 0.355 0.3583 0.3616 0.3648 0.3682 0.3715 0.3749 0.3783 0.3818 0.3853 0.3889 0.3964 0.4042 0.4126 0.4214 0.4309 0.4411 0.4523 0.4644 0.4778 0.4927 0.5386 0.6042 0.7078 0.9018 1.427 -

Sound Spd. [Btu/lb-F] (L)

3496 3327 3225 3151 3091 3041 2998 2959 2893 2837 2788 2749 2745 2705 2669 2636 2605 2575 2548 2522 2497 2473 2451 2429 2408 2388 2369 2350 2332 2315 2273 2234 2197 2162 2129 2098 2068 2039 2011 1984 1933 1886 1841 1798 1757 1718 1680 1644 1610 1576 1512 1451 1393 1338 1285 1234 1185 1137 1090 1045 935.2 830.2 727.9 626 519.7 -

Viscosity [lbm/ft-h] (L)

1.4832 1.2528 1.134 1.0584 1.0008 0.9576 0.9216 0.8892 0.8424 0.8028 0.7704 0.7602 0.7416 0.72 0.6984 0.6804 0.666 0.6516 0.6372 0.6228 0.612 0.6012 0.5904 0.5832 0.5724 0.5652 0.558 0.5508 0.5436 0.5364 0.5184 0.504 0.4932 0.4788 0.468 0.4572 0.45 0.4392 0.432 0.4248 0.4104 0.396 0.3852 0.3708 0.3636 0.3528 0.342 0.3348 0.3276 0.3204 0.306 0.2916 0.2808 0.27 0.2592 0.2484 0.2412 0.234 0.2232 0.216 0.198 0.18 0.1656 0.1476 0.1472 -

Therm. Cond. [Btu/h-ft-R] (L)

0.09941 0.09598 0.09384 0.09224 0.09095 0.08987 0.08893 0.0881 0.08666 0.08546 0.08442 0.0843 0.08348 0.08264 0.08187 0.08115 0.08049 0.07987 0.07929 0.07874 0.07822 0.07772 0.07724 0.07679 0.07635 0.07593 0.07552 0.07513 0.07475 0.07439 0.07351 0.0727 0.07194 0.07121 0.07053 0.06988 0.06926 0.06866 0.06809 0.06753 0.06649 0.06551 0.06458 0.0637 0.06287 0.06207 0.0613 0.06056 0.05985 0.05917 0.05785 0.05662 0.05544 0.05432 0.05324 0.0522 0.0512 0.05022 0.04928 0.04835 0.04613 0.04401 0.04198 0.04005 0.03987 -

(V)
99.84 102.1 103.5 104.6 105.5 106.2 106.8 107.4 108.3 109.1 109.8 110.0 110.4 110.9 111.4 111.8 112.3 112.6 113 113.3 113.6 113.9 114.2 114.5 114.7 114.9 115.2 115.4 115.6 115.8 116.3 116.7 117.1 117.4 117.8 118.1 118.3 118.6 118.9 119.1 119.5 119.9 120.2 120.5 120.7 121 121.2 121.3 121.5 121.6 121.8 122 122 122 122 121.9 121.8 121.6 121.4 121.1 120.1 118.9 117.1 114.8 111.3 90.2

(V)
0.3201 0.3081 0.3013 0.2966 0.293 0.2901 0.2876 0.2856 0.2821 0.2793 0.277 0.276 0.275 0.2733 0.2717 0.2703 0.2691 0.2679 0.2669 0.2659 0.265 0.2641 0.2633 0.2625 0.2618 0.2611 0.2605 0.2599 0.2593 0.2587 0.2574 0.2562 0.2551 0.2541 0.2531 0.2522 0.2514 0.2506 0.2498 0.2491 0.2478 0.2465 0.2454 0.2443 0.2433 0.2423 0.2414 0.2405 0.2396 0.2388 0.2372 0.2357 0.2342 0.2328 0.2314 0.23 0.2287 0.2273 0.226 0.2246 0.221 0.2172 0.213 0.2079 0.2012 0.1663

(V)
0.1567 0.1623 0.1663 0.1696 0.1725 0.175 0.1773 0.1795 0.1833 0.1867 0.1898 0.1926 0.1926 0.1952 0.1977 0.2 0.2023 0.2044 0.2064 0.2083 0.2102 0.212 0.2138 0.2155 0.2171 0.2188 0.2203 0.2219 0.2234 0.2249 0.2285 0.2319 0.2352 0.2385 0.2416 0.2447 0.2477 0.2507 0.2536 0.2565 0.2622 0.2678 0.2734 0.2789 0.2845 0.2901 0.2957 0.3015 0.3073 0.3132 0.3254 0.3381 0.3517 0.3661 0.3816 0.3984 0.4167 0.4368 0.4591 0.4839 0.5614 0.6738 0.854 1.196 2.119 -

(V)
518 528.2 534.2 538.4 541.7 544.3 546.5 548.3 551.3 553.6 555.5 556.0 557 558.3 559.4 560.3 561 561.7 562.2 562.7 563.1 563.4 563.7 563.9 564.1 564.2 564.3 564.4 564.4 564.4 564.4 564.1 563.8 563.4 562.9 562.3 561.7 561 560.3 559.6 557.9 556.2 554.3 552.4 550.4 548.3 546.2 544.1 541.9 539.6 535.1 530.4 525.7 520.9 516 511.1 506.1 501 495.9 490.8 477.6 464.1 450.1 435.1 418.2 -

(V)
0.019296 0.020268 0.020844 0.021312 0.021672 0.021996 0.022248 0.0225 0.022932 0.023292 0.02358 0.0239 0.023868 0.02412 0.024336 0.024552 0.024768 0.024948 0.025092 0.025272 0.025416 0.02556 0.025668 0.025884 0.026028 0.026172 0.02628 0.026424 0.026568 0.026712 0.027 0.027288 0.027576 0.027828 0.02808 0.028296 0.028548 0.028764 0.02898 0.02916 0.029556 0.029952 0.030312 0.030672 0.030996 0.03132 0.031644 0.031968 0.032256 0.032544 0.033156 0.033696 0.034272 0.034812 0.035388 0.035964 0.036504 0.03708 0.037692 0.038304 0.039924 0.04176 0.043992 0.046836 0.0468 -

(V)
0.00354 0.00377 0.00392 0.00404 0.00413 0.00422 0.00429 0.00435 0.00447 0.00457 0.00466 0.00492 0.00474 0.00481 0.00488 0.00494 0.00501 0.00506 0.00512 0.00517 0.00522 0.00527 0.00531 0.00536 0.00541 0.00546 0.00551 0.00555 0.0056 0.00564 0.00574 0.00584 0.00593 0.00602 0.00611 0.0062 0.00628 0.00637 0.00645 0.00653 0.00669 0.00685 0.00701 0.00717 0.00733 0.0075 0.00766 0.00784 0.00801 0.00819 0.00857 0.00897 0.0094 0.00986 0.01036 0.0109 0.01149 0.01212 0.01282 0.01358 0.01581 0.01865 0.02242 0.0278 0.03689 -

Application Guide AG 31-007

63

Appendix 3 Sample Pressure-Enthalpy Diagram

Pressure-Enthalpy Diagram for Refrigerant 134a
33

33

Copyright 2001, American Society of Heating, Refrigeration and AirConditioning Engineers, Inc www.ashre.org. Reprinted by permission from ASHRAE 2001 Handbook-Fundamentals
64 Application Guide AG 31-007

Post Office Box 2510, Staunton, Virginia 24402-2510 USA (800) 432-1342 www.mcquay.com