(Reinhard Radermacher, Yunho Hwang) Vapor Compress

Vapor
Compression
Heat Pumps
with Refrigerant
Mixtures
Reinhard Radermacher
Yunho Hwang
Boca Raton London New York Singapore
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Radermacher, Reinhard.
Vapor compression heat pumps with refrigerant mixes / Reinhard Radermacher, Yunho Hwang.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-3489-6 (alk. paper)
1. Heat pumps. 2. Refrigerants. I. Hwang, Yunho. II. Title.
TJ262.R33 2005
621.5′63--dc22 2005042099
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Preface
The authors strive to provide a comprehensive background and thorough understand-
ing of the thermodynamics of working fluid mixtures and their applications in vapor
compression systems. The information presented here is based on an extensive
review of the literature and includes a considerable body of experience gained by
the authors from over two decades of research in the laboratories of CEEE at the
University of Maryland, the National Institute of Standards and Technology (NIST),
and the Oak Ridge National Laboratory (ORNL). To ensure that this text is com-
prehensive and up to date, the authors invite all interested parties to submit correc-
tions, recommendations, and suggestions for improvement to Reinhard Radermacher
at [email protected] or Yunho Hwang at [email protected].
Acknowledgment
The partial support of this effort by the U.S. Department of Energy through Oak
Ridge National Laboratory (ORNL) and the University of Maryland is gratefully
acknowledged.
About the Authors
Dr. Yunho Hwang, a research associate professor at the University of Maryland’s
department of mechanical engineering, works with Dr. Radermacher in the Center
for Environmental Energy Engineering. Dr. Hwang’s career began as a senior
researcher at Samsung Electronics in Korea, and he has devoted more than 20 years
to university and private industry research. Dr. Yunho Hwang, Director of the Heat
Pump Laboratory (CEEE), is an internationally recognized expert in energy conver-
sion systems; in particular, heat pumping, air conditioning, and refrigeration systems.
He has coauthored 3 books and written more than 50 academic papers. He currently
serves as secretary of the IIR (International Institute of Refrigeration) Commission B2.
Dr. Reinhard Radermacher is a professor of mechanical engineering at the Uni-

versity of Maryland and director of the university’s Center for Environmental Energy
Engineering (CEEE). His engineering expertise, spanning over two decades, is
concentrated in energy conversion, renewable energy, heating and power systems,
and air conditioning and refrigeration.
Dr. Radermacher is a graduate of the Munich Institute of Technology, Germany,
and has worked with numerous private energy corporations, as well as government
institutions and engineering groups. He currently serves as editor of ASHRAE’s
(American Society of Heating, Refrigerating and Air-Conditioning Engineers)
HVAC&R Research Journal and associate editor of the International Journal of
Refrigeration. The author of more than 100 academic papers, Dr. Radermacher is
also coauthor of the books Heat Conversion Systems and Absorption Heat Pumps
and Chillers, both published by CRC Press.
NOMENCLATURE
17L Low Temperature Heating Test Based on ASHRAE Standard 116
35F Frost Accumulation Test Based on ASHRAE Standard 116
47S High Temperature Heating Test Based on ASHRAE Standard 116
47C Cyclic Heating Test Based on ASHRAE Standard 116
A Heat Exchanger Area
AREP Alternative Refrigerant Evaluation Program
ARI Air-Conditioning and Refrigeration Institute, Arlington, VA
ASHRAE American Society of Heating, Refrigerating and Air-Conditioning
Engineers, Inc.
AT Approach Temperature
Bo Boiling Number
CD Cyclic Degradation Coefficient
CFC Chlorofluorocarbon
CLF Cooling Load Factor
CP Critical Point
cp Isobaric Specific Heat
COP Coefficient of Performance
CSPF Cooling Seasonal Performance Factor
D Tube Diameter
DOE Department of Energy
DGWP Direct Global Warming Potential
E Enhancement Factor
EB Energy Balance between Water-side and Refrigerant-side
EPA Environmental Protection Agency
f Frictional Coefficient
Fr Froude Number
G Mass Flux
g Acceleration of Gravity
GWP Global Warming Potential
h Enthalpy or Heat Transfer Coefficient
HCFC Hydrochlorofluorocarbon
HFC Hydrofluorocarbon
HLF Heating Load Factor
HSPF Heating Seasonal Performance Factor
HTC Heat Transfer Coefficient
HX Heat Exchanger
ID Inside Diameter
IDLH Immediately Dangerous to Life or Health, maximum level from which
one could escape within 30 minutes without impairing symptoms or
any irreversible health effects
IGWP Indirect Global Warming Potential
k Thermal Conductivity
LMTD Log Mean Temperature Difference
LPE Liquid Precooling in Evaporator
M Molecular Weight
.
m Mass Flow Rate
N Number or Polytropic Index
NIST National Institute of Science and Technology
NTU Number of Transfer Unit
Nu Nusselt Number
OD Outside Diameter
ODP Ozone Depletion Potential
ORNL Oak Ridge National Laboratory
P Pressure
Pr Reduced Pressure
Pr Prandtl Number
Q Capacity
R407C R32/R125/R134a mixture in compositions of 23/25/52 wt.%
R410A R32/R125 (50/50 wt.%)
R410B R32/R125 (45/55 wt.%)
Re Reynolds Number
RT Refrigeration Ton
s Entropy
S Suppression Factor
SEER Seasonal Energy Efficiency Ratio
SPF Seasonal Performance Factors
SLHX Suction-Line Heat Exchanger
ST Short Tube Restrictor
T Temperature
TEV Thermostatic Expansion Valve
TLV Threshold Limit Value, the refrigeration concentration limit in the air
for a normal 8-hour workday that will not cause an adverse effect in
most people.
U Overall Heat Transfer Coefficient
VFR Volume Flow Rate
Xtt Martinelli Parameter
x Mass Fraction
xq Vapor Quality
∆P Pressure Drop
SUBSCRIPT DESIGNATIONS
a air
amb ambient
avg average
b bulk flow or bubble point
bc bulk convection
c cross-section
cp critical point
cal calculated
co condenser
cyc cyclic
d dew point
dis compressor discharge
e evaporation
ev evaporator
exp experimental
f fin
fg liquid vapor
gc gas cooler
i mean integrated
in inlet
isen isentropic
l liquid
mec mechanical
MN Martinelli-Nelson
mot motor
nb nucleate boiling
o wall or overall
opt optimum
out outlet
pol polytropic
pool pool boiling
r refrigerant
sat saturation
sub subcooling at the condenser outlet
suc compressor suction
sup superheating at the evaporator outlet
sv saturated vapor
t total
tp two-phase
v vapor
vol volumetric
w water or wall
GREEK SYMBOLS
µ dynamic viscosity
ρ density
σ surface tension
φ two-phase heat transfer multiplier
α void fraction, Avapor / Across-sectional
Table of Contents
Chapter 1 Introduction ..........................................................................................1
1.1 Heat Pumping...................................................................................................1
1.2 Overview of Current Products ......................................................................... 4
1.2.1 Residential Air Conditioners and Heat Pumps....................................4
1.2.2 Commercial Air-Conditioning Systems............................................... 5
1.2.3 Industrial Systems ................................................................................5
1.2.4 Refrigeration Systems .......................................................................... 5
1.3 History of Working Fluids ...............................................................................6
1.4 Requirements for Working Fluids ...................................................................9
1.5 Background of Environmental Concerns.......................................................10
1.5.1 Impact of Ozone Depletion................................................................10
1.5.2 Impact of Global Warming ................................................................10
1.5.3 International Efforts on Environmental Protection ........................... 11
1.5.4 Impact of Environmental Issues on U.S. Climate Control
Industry...............................................................................................11
1.5.5 Mixtures as R22 Replacements ......................................................... 11
References................................................................................................................12
Chapter 2 Properties of Working Fluids.............................................................17

2.1 Thermodynamic Diagrams of Pure and Mixed Refrigerants........................17
2.1.1 Temperature-Mass Fraction Diagram ................................................18
2.1.2 Pressure-Temperature Diagram.......................................................... 24
2.1.3 Pressure-Enthalpy Diagram ...............................................................27
2.1.4 Temperature-Entropy Diagram ..........................................................42
2.1.5 Temperature-Enthalpy Diagram.........................................................43
2.1.6 Pressure-Mass Fraction Diagram....................................................... 44
2.2 Analytical Treatment of Thermodynamic Properties ....................................47
2.2.1 Types of Substances in Internal Equilibrium ....................................47
2.2.2 Definitions of Concentration..............................................................48
2.2.3 Solubility ............................................................................................48
2.2.4 Liquid Mixing Phenomena ................................................................49
2.2.5 Adiabatic Mixing of Binary Mixtures ...............................................53
2.2.6 Isothermal Mixing of Binary Mixtures .............................................55
2.2.7 Mixing of Binary Mixtures with Heat Exchange..............................56
2.2.8 Specific Heat of Binary Mixtures......................................................56
2.2.9 Latent Heat of Binary Mixtures ........................................................57
2.2.10 Critical Point of Binary Mixtures......................................................58
2.3 Ternary and Multicomponent Mixtures.........................................................59
2.3.1 Thermodynamic Diagrams for Multicomponent Mixtures ...............60
2.3.2 Flammability of Mixtures .................................................................. 61
2.3.3 Reasoning for Selecting Certain Mixtures ........................................ 61
References................................................................................................................ 63
Chapter 3 Vapor Compression Cycle Fundamentals..........................................65

3.1 The Carnot Cycle ...........................................................................................65
3.2 Heat Pumps in the Context of Energy Conversion .......................................67
3.3 The Ideal Vapor Compression Cycle.............................................................69
3.3.1 Power and Capacity Calculations ......................................................72
3.4 Differences between the Carnot Cycle and Vapor Compression Cycle .......73
3.5 Realistic Vapor Compression Cycles.............................................................77
3.6 Lorenz Cycle ..................................................................................................79
3.7 Vapor Compression Cycle with Zeotropic Mixtures in Thermodynamic
Diagrams ........................................................................................................82
3.7.1 Pressure-Temperature Diagram..........................................................82
3.7.2 Pressure-Enthalpy Diagram ...............................................................83
3.7.3 Temperature-Entropy Diagram ..........................................................85
3.7.4 Temperature-Mass Fraction Diagram ................................................86
3.8 The Matching of Temperature Glides............................................................87
3.9 Methods for Comparing the Performance of Pure and Mixed
Refrigerants ....................................................................................................90
3.10 Simulation of the Vapor Compression Cycle ................................................93
3.10.1 Refrigeration Component Models .....................................................93
3.10.1.1 Heat Exchanger Model .......................................................93
3.10.1.2 Compressor Model............................................................ 104
3.10.1.3 Expansion Device Model .................................................106
3.10.1.4 Refrigerant Mixture Properties.........................................109
3.10.2 Cycle Models ...................................................................................110
3.10.2.1 NIST Model: Cycle 7 and Cycle 11 ................................110
3.10.2.2 Binary Mixture Performance Analysis.............................112
3.10.2.3 Refrigerant Performance Comparison..............................115
3.10.2.4 ORNL Model: BICYCLE and Mark V............................120
3.10.2.5 University of Maryland Model: HAC1 and HPCYCLE...124
References..............................................................................................................129
Chapter 4 Methods for Improving the Cycle Efficiency..................................135

4.1 Measures of Incremental Efficiency Improvement .....................................135
4.2 The Suction Line to Liquid Line Heat Exchanger......................................138
4.3 The Economizer ...........................................................................................142
4.4 The Expander ...............................................................................................145
4.5 The Three-Path Evaporator..........................................................................146
References..............................................................................................................147
Chapter 5 Experimental Performance Measurements ......................................149
5.1 Laboratory Breadboard Tests.......................................................................149
5.1.1 NIST Breadboard Heat Pump I .......................................................150
5.1.1.1 Test Facility.......................................................................150
5.1.1.2 Capacity Measurements....................................................150
5.1.1.3 Test Procedure ..................................................................153
5.1.1.4 Heat Exchanger Variations ...............................................154
5.1.1.5 Linearity of the Enthalpy vs. Temperature Relationship ...157
5.1.1.6 Liquid Precooling in Evaporator ......................................160
5.1.1.7 Discussion .........................................................................161
5.1.1.8 Conclusion ........................................................................162
5.1.2 NIST Breadboard Heat Pump II......................................................163
5.1.2.1 Test Facility.......................................................................163
5.1.2.2 Test Results of Test Apparatus II .....................................163
5.1.2.3 Conclusion ........................................................................170
5.1.3 ORNL Breadboard Heat Pump........................................................170
5.1.3.1 Test Facility....................................................................... 170
5.1.3.2 R13B1/R152a Test............................................................171
5.1.3.3 R143a/R124 Test...............................................................171
5.1.3.4 R143a/R124 and R32/R124 Test...................................... 174
5.2 Actual System Tests Experience..................................................................177
5.2.1 Heat Pump Test at CEEE.................................................................177
5.2.1.1 Test Facility....................................................................... 177
5.2.1.2 Test Unit............................................................................181
5.2.1.3 Refrigerants Investigated ..................................................182
5.2.1.4 Test Procedure .................................................................. 184
5.2.1.5 Test Results ....................................................................... 185
5.2.1.6 Effects of Heat Exchanger Geometry on Mixture
Performance ......................................................................190
5.2.2 Heat Pump Test at NIST.................................................................. 191
5.2.2.1 R13B1/R152a Test............................................................195
5.2.2.2 R32/R134a Test.................................................................198
References.............................................................................................................. 206
Chapter 6 Refrigerant Mixtures in Refrigeration Applications........................209

6.1 Single Evaporator Refrigeration Cycle........................................................209
6.2 Dual Evaporator Refrigeration Cycle .......................................................... 212
6.3 Lorenz-Meutzner Cycle ............................................................................... 213
6.4 Modified Lorenz-Meutzner Cycle Refrigerator...........................................215
References.............................................................................................................. 218
Chapter 7 Refrigerant Mixtures in Heat Pump Applications...........................221

7.1 Capacity Control .......................................................................................... 221
7.1.1 One Accumulator Cycle................................................................... 222
7.1.2 Two Accumulators Cycle................................................................. 223
7.1.3 Modified Two Accumulators Cycle .................................................226
7.1.4 Three Accumulators Cycle............................................................... 227
7.1.5 Cycle with Rectifier .........................................................................227
7.1.6 Modified Cycle with Rectifier ......................................................... 228
7.1.7 Cycle with Rectifier-Accumulator ...................................................229
7.2 R22 Replacement .........................................................................................230
7.2.1 Screen of Refrigerant Mixtures ....................................................... 230
7.2.2 Screen of HFC Refrigerant Mixtures ..............................................232
References..............................................................................................................235
Chapter 8 Heat Transfer of Refrigerant Mixtures ............................................237

8.1 Nucleate Pool Boiling Heat Transfer Coefficients ...................................... 237
8.2 Flow Boiling Heat Transfer Coefficients..................................................... 239
8.3 Correlations for Flow Boiling Heat Transfer ..............................................245
8.3.1 Superposition Models ......................................................................246
8.3.1.1 Chen Correlation...............................................................246
8.3.1.2 Bennett and Chen Correlation ..........................................247
8.3.1.3 Gungor and Winterton Correlation...................................248
8.3.1.4 Jung Correlation................................................................ 248
8.3.2 Enhancement Models.......................................................................249
8.3.2.1 Shah Correlation ...............................................................249
8.3.2.2 Schrock and Grossman Correlation .................................250
8.3.2.3 Mishra Correlation............................................................250
8.3.2.4 Sami Correlation...............................................................251
8.3.2.5 Shin Correlation................................................................251
8.3.3 Asymptotic Models ..........................................................................252
8.3.3.1 Liu and Winterton Correlation ......................................... 252
8.3.3.2 Wattelet Correlation..........................................................252
8.3.3.3 Bivens and Yokozeki Correlation .....................................253
8.3.4 Comparison of Correlations.............................................................254
8.4 Pressure Drop During Evaporation..............................................................254
8.4.1 Martinelli and Nelson Correlation...................................................254
8.4.2 Singal Correlation ............................................................................257
8.4.3 Sami Correlation ..............................................................................258
8.4.4 Jung and Radermacher Correlation ................................................. 258
8.4.5 Souza and Pimenta Correlation .......................................................259
8.4.6 Other Studies....................................................................................259
8.5 Condensation Heat Transfer Coefficients .................................................... 259
8.6 Correlations for Flow Condensation Heat Transfer ....................................264
8.6.1 Akers Correlation .............................................................................264
8.6.2 Traviss Correlation...........................................................................265
8.6.3 Shah Correlation .............................................................................. 265
8.6.4 Dobson Correlation ..........................................................................266
8.6.5 Tandon Correlation........................................................................... 266
8.6.6 Koyama Correlation .........................................................................267
8.6.7 Sami Correlation .............................................................................. 267
8.6.8 Sweeney Correlation ........................................................................267
8.6.9 Comparison of Correlations............................................................. 268
8.7 Pressure Drop during Condensation ............................................................ 268
8.7.1 Koyama Correlation ......................................................................... 270
8.7.2 Sami Correlation ..............................................................................272
8.7.3 Other Studies.................................................................................... 272
References..............................................................................................................273
Chapter 9 Operational Issues ............................................................................279

9.1 Regulation .................................................................................................... 279
9.1.1 Clean Air Act Amendments of 1990 ...............................................279
9.1.2 EPA Regulations .............................................................................. 279
9.2 Refrigerant Recovery ...................................................................................280
9.3 Cycle Flushing ............................................................................................. 281
9.4 Refrigerant Mixing.......................................................................................282
9.5 Refrigerant Mass Fraction Measurement ....................................................283
9.6 Evacuating a System .................................................................................... 284
9.7 Refrigerant Charge ....................................................................................... 285
9.8 Leak Checking .............................................................................................287
9.9 Mass Fraction Shifts .................................................................................... 287
9.9.1 Mass Fraction Shift in the Cycle..................................................... 289
9.9.2 Mass Fraction Shift Due to Leakage...............................................294
9.9.3 Mass Fraction Shift during Container Transfers .............................297
References.............................................................................................................. 297
1 Introduction
Due to growing environmental awareness and resulting concerns, refrigerants — the
working fluids for refrigeration systems, heat pumps and air conditioners — have
gained considerable attention. Well-known, proven fluids were banned and replaced
with new ones. In the process, refrigerant mixtures were introduced to achieve
acceptable properties reasonably well-matched to those of the fluids to be replaced.
The thermodynamics of mixtures is considerably more complex than that of pure
fluids. This text is dedicated to introducing the thermodynamic theory and back-
ground of working fluid mixtures and their practical implementations. It discusses
the opportunities and challenges and aims at providing the practicing engineer, as
well as the aspiring engineering student, with all the necessary information to
successfully design systems that take the best possible advantage of fluid mixtures.
Emphasis is placed on practical experience from laboratory investigations.
1.1 HEAT PUMPING

On many occasions, a fluid needs to be cooled below the temperature of the sur-
roundings. Examples are the production of chilled water or brine for air-conditioning
and refrigeration purposes or the cooling of air to condition a space. In this context,
the term “cooling” usually implies a certain quantity of energy is extracted from a
fluid while reducing its temperature. This energy is rejected to a second fluid at a
higher temperature than that of the first fluid. For example, in a domestic refrigerator,
energy is extracted from the air inside the cabinet, reducing its temperature and
cooling the cabinet. In turn, energy is rejected from the refrigeration unit to the
surrounding air, heating the exterior. When energy transfer is based on a temperature
gradient, one speaks of heat transfer. In this strict sense, “heat” exists only as long
as a temperature gradient enables this transfer of energy. However, in the field of
refrigeration and air-conditioning, the term “heat” is used more loosely and is
understood as energy in more general terms. This text adheres to this latter convention.
In general, the machines that accomplish the lift of a certain quantity of energy
from a lower temperature level to a higher one are termed heat pumps. The thermo-
dynamic processes involved in heat pumping are governed by the First and Second
Laws of Thermodynamics. The First Law is the conservation of energy and reads
∑Q + W = 0
i (1.1)
where Q stands for the amounts of heat exchanged at various temperature levels Ti
and W for the amount of work that is required in the process.
1
2 Vapor Compression Heat Pumps with Refrigerant Mixtures
The Second Law states that heat cannot flow from a lower to a higher temperature
without the expenditure of energy. One way of expressing this statement is shown
in the following equation.
∑ QT = 0 for reversible processes

i
i
(1.2)
Equation 1.1 is based on the assumption that the energy supplied to a system is
counted as positive.
Figure 1.1.1 illustrates the situation. The vertical axis is the temperature axis
with increasing temperature from the bottom to top, i.e., T1 < T2. A certain amount
of heat is removed by the device M at temperature T1 and, by using work that is
supplied to M, heat is rejected at T2. The amount of heat rejected is the sum of the
amount of work W required by M and the amount of heat removed at T1. This is a
consequence of the First Law,
Q1 + W = Q2 (1.3)
However, does this relationship of Figure 1.1.1 fulfill the Second Law, Equation 1.2?
Applying Equation 1.2 to the situation of Figure 1.1.1 yields
Q1 Q2
− =0 (1.4)
T1 T2
and using Equation 1.3,
Q1 Q1 + W
− =0 (1.5)
T1 T2
T2
Q 2 = Q 1+ W
M W
Q1
T1
FIGURE 1.1.1 Heat Pumping — The process of lifting energy Q1 from a temperature level
T1 to T2, releasing Q2. The input of energy, in this case work W, is required.
Introduction 3
After rearranging the terms, we find
Q1 Q1 W
− − =0 (1.6)
T1 T2 T2
Since T2 > T1, the difference of the first two terms is still larger than zero. Equation
1.6 requires that the Second Law is fulfilled only if the work input is sufficiently
large. Thus, there is a minimum work requirement. This minimum amount of work
is required for the system to operate reversibly. The Second Law does not say
anything about an upper limit for the work, so the system may be very inefficient
and operate irreversibly if W becomes much larger than necessary. There is no upper
limit on the degree of irreversibility for the heat pumping operation.
The First and Second Laws state for lifting heat from one temperature level to
a higher one, the expenditure of energy is required and that the amount of energy
rejected at the higher temperature level is the sum of the heat removed from the
lower temperature level plus the energy added to accomplish the lift. The energy
required to drive the system can be supplied in the form of work, as assumed here,
or it can be supplied in the form of heat. Examples are absorption heat pumps,
desiccant systems and engine-driven heat pumps.
One of the most common implementations of a heat pump is shown in Figure
1.1.2. Liquid refrigerant evaporates in the evaporator at a given pressure level while
it absorbs heat. In other terms, this is the cooling effect. The compressor compresses
the vapor that exits from the evaporator and delivers the compressed, high-pressure
vapor to the condenser where the vapor is cooled and condensed. The liquefied vapor
leaves the condenser and enters the expansion valve. This valve reduces the pressure
level and meters the fluid so that as much refrigerant enters the evaporator as the
compressor removes.
The concept shown in Figure 1.1.2 represents a vapor compression heat pump.
It is the underlying concept of the type of heat pumps discussed in this text. All of these
systems have to fulfill the First and Second Law in the form of the Equations 1.1 and 1.2.
It should be noted that although both the First and Second Law must be observed
in heat pump design, the reader will notice that in subsequent chapters energy and
Condenser
Expansion
Va lve Compressor
Evaporator
FIGURE 1.1.2 Schematic of a vapor compression heat pump (or refrigeration system).
mass balances are discussed but rarely entropy balances. This implies that the Second
Law could be violated in idealized situations. However, in all examples we are using
measured data of actual working fluids that do exist. These data inherently ensure
that the Second Law is not violated.
The following sections provide an overview of various heat pump applications.
Note that whenever energy is lifted from a lower temperature to a higher temperature,
we speak in general of a heat pumping process. However, for many applications, the
process is not as important as its result. In all refrigeration and air-conditioning
applications, energy is removed from a lower temperature level and rejected at a
higher temperature level. The main effect that interests the user is the refrigeration
or cooling effect, i.e., heat removal. On the other hand, in what is customarily called
heat pumping, the user is interested in the heat delivered at the high temperature level.
In both cases, the underlying thermodynamic process is the same; only the applica-
tion or the desired benefit are different. In this text, the term heat pumping is used as
the general description for the thermodynamic process independent of the application.
The terms refrigeration and air-conditioning refer specifically to the application.
1.2 OVERVIEW OF CURRENT PRODUCTS

Vapor compression heat pump systems have found many applications spanning a
wide range of capacities. This chapter will give an overview of applications, system
configurations and the economic importance of vapor compression systems.
The global market for air-conditioning and refrigeration equipment is estimated
to be $42 to 45 billion, with the United States and Japan each covering one third of
the worldwide production followed by Europe and China. In terms of applications,
the market is split into thirds as well. One third covers residential air-conditioning,
one-third refrigeration (mostly food preservation), and one-third commercial air-
conditioning. In the United States, stationary refrigeration and air-conditioning systems
are used for 45 million homes and commercial buildings as well as 100 million
refrigerators and 30 million freezers. Mobile refrigeration and air-conditioning sys-
tems are used for 90 million air-conditioned cars and trucks and 200,000 refrigerated
trucks and rail cars. In 1985, approximately 420 million pounds of refrigerants were
used for these applications.
1.2.1 RESIDENTIAL AIR CONDITIONERS AND HEAT PUMPS

In the United States, residential air-conditioning has become very common and is
even used in the colder regions of the north. The units are usually “split” systems,
referring to the fact that the air conditioner is split into two units. The evaporator
together with the expansion device is located inside the building and the condensing
unit, consisting of compressor and condenser, is located outside. The piping con-
nection is installed in the field, which is also where the system is charged with
refrigerant. The cooling capacity ranges from 3 to 18 kW (1 to 5 refrigeration tons).
Around 18% of these units are designed as so-called heat pumps (ARI, 2000). They
have a four-way reversing valve that allows the same unit to serve as an air condi-
tioner in the summer months and as a heat pump in the winter. Since traditionally
Introduction 5
the system is designed and sized for the air-conditioning function, the heat pumps
turn out to have insufficient heating capacity in most climates. Supplemental heat
in the form of electric or gas heat is usually required.
Another form of residential air-conditioning is the window air conditioner. It is
designed to cool just one room and the largest capacity usually does not exceed
7 kW (2 refrigeration tons). All the components are integrated within one chassis
that is usually mounted within the frame of a window.
1.2.2 COMMERCIAL AIR-CONDITIONING SYSTEMS

Commercial air-conditioning systems span a wide range of capacities from 17 kW
(5 refrigeration tons) to several thousand tons. The larger ones usually employ
variable speed centrifugal compressors and low-pressure refrigerants for high effi-
ciencies. They are designed to produce chilled water at about 5 to 7˚C and are cooled
by water that in turn rejects heat to the ambient in a wet cooling tower. The chilled
water is supplied to air-handling units located throughout the building.
It is interesting to note that many commercial buildings require cooling year-
round because these buildings have considerable internal heat loads resulting from
the presence of occupants and equipment that generate heat. A considerable floor
area of useful space is located within the core of the building. This interior space
is surrounded by other rooms that have outside walls but these perimeter rooms are
always maintained at a constant temperature. Thus, the interior space has no way
of rejecting heat and requires cooling year-round. In newer systems, a so-called
economizer allows the use of outdoor air for core cooling whenever weather con-
ditions are suitable.
Recently, a new generation of chillers emerged that are vapor compression cycles
driven by internal combustion engines. The primary energy input is gas rather than
electricity and the new generation chillers reduce the reliance on costly peak power
and help to avoid high demand charges.
For smaller buildings or those with a limited number of stories, so-called rooftop
units are used. These are air-conditioning systems that reach up to 700 kW (200
refrigeration tons) in capacity and have the air handler integrated within the unit,
often including a heating device such as a gas furnace.
1.2.3 INDUSTRIAL SYSTEMS

Industrial refrigeration systems serve a wide range of purposes. They include food
storage in large warehouses to the provision of cold utilities in chemical plants,
refineries and polymer production facilities. Further, many production facilities such
as printing, spinning, electronics and precision machining require very stringently
controlled thermal environments. Many machines for industrial refrigeration and air-
conditioning are custom-manufactured to meet specific criteria.
1.2.4 REFRIGERATION SYSTEMS

Probably the most important and earliest application of refrigeration technology was
that of food storage. Today, the technology has developed into a complete cold chain
in which food products such as fish, meats, dairy products and vegetables are cooled
or refrigerated from the moment of harvest or production through storage, transport,
wholesale and retail to the consumer, who uses the residential refrigerator as the
last storage facility in this chain. Accordingly, a wide range of refrigeration systems
have been developed that meet the various needs.
The domestic refrigerator is a unique device in that it has reached such a level
of maturity that some units last more than 20 years without ever failing or requiring
maintenance. In addition, the energy consumption has been reduced by more than
a factor of two over the past 30 years. The newest models of a typical refrigerator
for a U.S. household show a power consumption that is equivalent to that of a 50
W light bulb left on continuously.
Refrigeration systems in supermarkets usually have central compressor plants
with multiple compressors in parallel that serve the same set of evaporators. The
evaporators are located throughout the store in the display cabinets for frozen or
refrigerated foods. As a consequence, a single store can boast miles of refrigerant
piping. Due to the length of piping and the many inherent piping connections,
supermarket refrigeration systems tended to lose considerable amounts of refrigerant.
With the advent of environmental concerns and improved quality standards, these
leakages have been reduced considerably. New systems are under consideration in
which the refrigerant does not leave the machine room. Rather, a secondary refrigerant
is used to cool the display cabinets. This measure reduces refrigerant leakage and
increases system reliability, but may contribute to a reduction in energy efficiency.
Transport refrigeration systems, especially those that are trailer or container
mounted, must come with their own power supply, usually a small diesel or gas
engine. Systems must be especially robust to withstand the high vibration levels.
Also, these systems must be designed to cover a wide range of operating conditions.
The transported goods may require storage temperatures ranging from –40 to 20˚C
while the ambient temperature can span even a wider range of temperatures.
For food preservation, there are also a wide array of specialized required cooling
systems. Examples are milk coolers on farms, cooling systems for tank trucks and
refrigeration systems ranging from fish trawlers to wine coolers.
The air-conditioning of cars has become an expected feature in the United States
and many developed and developing countries. The cooling capacity varies over a
wide range because the compressor is directly coupled to the engine and the com-
pressor revolutions vary with that of the engine. Furthermore, due to vibration and
the need to use flexible hoses to connect the components that are mounted on the
car and those mounted on the engine block, these systems traditionally have a
relatively high rate of refrigerant leakage. With the advent of environmental con-
cerns, the leakage rates have been reduced dramatically.
1.3 HISTORY OF WORKING FLUIDS

The First and Second Laws state only the conditions and limitations under which
machinery such as refrigeration systems can operate. The actual implementation is
not prescribed by these laws. It is common practice in the refrigeration industry to
employ the vapor compression cycle of Figure 1.1.2. To do so requires the use of
Introduction 7
working fluids, commonly termed refrigerants. They represent one of the key ingre-
dients of any vapor compression system and influence design, operation and cost
immensely. A short overview of the historical development of refrigerants follows
that provides insight into the development of the refrigeration systems. The following
is an excerpt of a paper presented by Calm and Didion in 1997.
Refrigeration goes back to ancient times, using stored ice and a number of
evaporative processes. Early in the 19th century, the use of a volatile fluid in a closed
cycle was proposed by Oliver Evans. He used evaporating ether, under a vacuum,
and then pumped the vapor to a water-cooled heat exchanger to be condensed for
reuse.
Other refrigerants were introduced in the 1830s with the invention of the vapor-
compression machine by Perkins. He designed a machine to use sulfuric (ethyl)
ether as the refrigerant (Perkins, 1834). The first machine actually used caoutchou-
cine, an industrial solvent that Perkins apparently utilized in his business as a printer.
It seems the first tradeoff in refrigerants — and one still driving selections — was
based on availability.
Table 1.1 summarizes the historic introduction of refrigerants. The years given
serve only as guidelines, since the period from the introduction of a new fluid to its
generally accepted use always spans a number of years. Table 1.1 summarizes early
refrigerants, namely those predating fluorinated chemicals and state-of-the-art fluoro-
chemicals that are under consideration today. Downing (1988), Nagengast (1989
and 1996) and Thévenot (1979) present further details.
The first century of refrigerant use was dominated by innovative efforts with
familiar fluids. The goals were to provide refrigeration and, later, to improve machine
durability. Use of blends was attempted where single-compound solutions could not
be found (Pictet, 1885). After World War I, attention turned to safety and performance
as well. Willis H. Carrier and R.W. Waterfill initiated one of the first documented
systematic searches (Carrier and Waterfill, 1924). They investigated a range of
candidate refrigerants for suitability for both positive displacement and centrifugal
compression machines. These analyses closely examined ammonia, ethyl ether,
carbon dioxide, carbon tetrachloride, sulfur dioxide and water. They finally selected
dielene (1,2-dichloroethene, R1130) for the first centrifugal machine, though an
international search was needed to find a source for it (Ingels, 1952).
Nearly all of the early refrigerants were flammable, toxic or both, and some
were also highly reactive. Accidents were common. For perspective, propane was
marketed as the odorless safety refrigerant (CLPC, 1922).
The discovery of fluorinated refrigerants began with Thomas Midgley, Jr., in
1928 (Midgley, 1937). Midgley and his associates, Albert L. Henne and Robert R.
McNary, scoured property tables to find chemicals with the desired boiling point.
They restricted the search to those known to be stable but not toxic or flammable.
They eventually used organic fluorides. While fluorine was known to be toxic by
itself, Midgley and his collaborators felt that compounds containing it could be
nontoxic.
Recognizing the deficiencies of the published literature, Midgley, Henne and
McNary turned to the periodic table of the elements. They quickly eliminated those
elements yielding insufficient volatility and then eliminated those resulting in unstable
TABLE 1.1
Introduction of Refrigerants
Year Refrigerant Chemical Makeup, Formula
1830s Caoutchoucine Distillate of india rubber

CH3–CH2–O–CH2–CH3
1840s Methyl ether (RE170) CH3–O–CH3
1850 Water/sulfuric acid H20/H2SO4
1856 Ethyl alcohol CH3–CH2–OH
1859 Ammonia/water NH3 /H20
1866 Chymogene Petrol ether and naphtha (hydrocarbons)
Carbon dioxide CO2
1860s Ammonia (R717) NH3CH3(NH2)
Methyl amine (R630) CH3–CH2(NH2)
Ethyl amine (R631)
1870 Methyl formate (R611) HCOOCH3
1875 Sulfur dioxide (R764) SO2
1878 Methyl chloride (R40) CH3CL
1870s Ethyl chloride (R160) CH3–CH2CL
1891 Blends of sulfuric acid with hydrocarbons H2SO4, C4H10, C5H12, (CH3)2CH–CH3
1900s Ethyl bromide (R160B1) CH3–CH2Br
1912 Carbon tetrachloride CCl4
Water vapor (R718) H2O
1920s Isobutane (R600a) (CH3)2CH–CH3
Propane (R290) CH3–CH2–CH3
1922 Dielene (R1130a) CHClCHCl
1923 Gasoline Hydrocarbons
1925 Trielene (R1120) CHClCCl2
1926 Methylene chloride (R30) CH2Cl2
1931 R12 CF2Cl2
1932 R11 CFCl3
1960s R22 CF2ClH
1980s R123 CF3CCl2H
1980s R124 CF3CFClH
1980s R125 CF3CF2H
1990s R134a CF3CFH2
1990s R407C R32/R125/R134a 23/25/52 wt.%
1990s R410A R32/R125 50/50 wt.%
1990s R404A R125/R143a/R134a 44/52/4 wt.%
and toxic compounds as well as the inert gases, based on their low boiling points.
They were left with just eight elements: carbon, nitrogen, oxygen, sulfur, hydrogen,
fluorine, chlorine and bromine. These elements clustered at an intersecting row and
column of the periodic table of the elements, with fluorine at the intersection.
Midgley and his colleagues then made three interesting observations. First,
flammability decreases from left to right for the eight elements. Second, toxicity
generally decreases from the heavy elements at the bottom to the lighter elements
Introduction 9
at the top. And third, every known refrigerant at the time was made from combinations
of those elements. The historical fluids actually comprised only seven of the eight
Midgley elements, since there appears to be no record of prior use of refrigerants
containing fluorine.
The first publication on fluorochemical refrigerants shows how chlorination and
fluorination of hydrocarbons can be varied to provide desired boiling points (Midgley,
1930). This paper also shows how the composition of the molecule influences relative
flammability and toxicity. Commercial production of R12 began in 1931, followed
by R11 in 1932 (Downing, 1966 and 1984).
Other investigators have repeated Midgley’s search with newer methods and
modern databases and have come to similar findings. McLinden and Didion (1987)
documented an extensive screening of industrial chemicals. Of the chemicals meet-
ing their criteria, all but two — both highly reactive and toxic — contained the
Midgley elements.
1.4 REQUIREMENTS FOR WORKING FLUIDS

Refrigerants are expected to meet certain criteria in order to be found acceptable by
industry and users. However, with increasing environmental concerns, the set of
criteria increases. It becomes more and more difficult to find fluids that meet all or
even most requirements. Future refrigerant choices will always be a compromise.
The following criteria should be fulfilled:
• Lack of corrosion, chemically inert. Refrigerants should not corrode any

construction materials present in the system. Also, they should not react
with any fluids in the system (such as compressor lubricants).
• Lack of toxicity. For the safety of manufacturing and service personnel,
refrigerants must be nontoxic.
• Nonflammable. To avoid accidents caused by any sources of intense heat
or ignition (such as propane torches used by repair personnel or sparks
generated by electrical equipment), it is generally required that refriger-
ants are nonflammable and not explosive except when the quantities are
below prescribed limits.
• Environmentally safe. Refrigerants should not affect or alter environmen-
tal conditions in any way. One important aspect of that requirement is
that refrigerants should show high energetic efficiency. The lack thereof
would lead to increased production of carbon dioxide at the power plant
and thus contribute indirectly to the global warming process.
• Thermodynamic requirements. The thermodynamic properties of refrig-
erants have to fulfill certain criteria that will be discussed in Chapter 2.
The overall goal is to achieve energy conversion efficiency and sufficient
capacity.
Thus, refrigerants must be safe locally and globally. To be safe locally means
fluids should be nontoxic and nonflammable and pose no danger of explosion. They
must also not affect any construction materials. These criteria aim at safety during
operation, manufacture, service, use and final disposal. To be safe globally means
refrigerants should not affect the environment in a significantly negative way.
In order to meet these requirements, an increasing effort is made to use refrig-
erant mixtures. They offer the potential to be the best compromise for fluids that
meet some of the thermodynamic requirements that are very important for the
performance of the equipment and hopefully all the other requirements that deter-
mine feasibility in many different aspects. Refrigerant mixtures are gaining impor-
tance as the acceptable working fluid of future generations of equipment. However,
the thermo-physical properties of mixtures are considerably more complex than
those of pure fluids. It is the focus of this text to comprehensively present the
characteristics of mixtures to the advanced student and practicing engineer.
1.5 BACKGROUND OF ENVIRONMENTAL CONCERNS

1.5.1 IMPACT OF OZONE DEPLETION
Stratospheric ozone depletion and global warming threaten to become the dominant
environmental issues. Chlorofluorocarbons (CFCs) and other ozone-depleting sub-
stances that leak from refrigeration and air-conditioning equipment migrate to the
stratosphere and deplete the ozone layer. Current ozone depletion at mid-latitudes
is estimated as approximately 5%. Ozone depletion harms living creatures on Earth,
increases the incidence of skin cancer and cataracts and poses risks to the human
immune system. A sustained 1% decrease in stratospheric ozone will result in
approximately a 2% increase in the incidence of fatal non-melanoma skin cancer
based on a United Nations Environment Program study. The U.S. Environmental
Protection Agency (EPA) expects 295 million fewer cases of non-melanoma skin
cancer over the next century with a successful phaseout of CFCs.
1.5.2 IMPACT OF GLOBAL WARMING

The anthropogenic use of energy has been adding gases to the atmosphere that trap
heat radiation and warm the earth, known as “greenhouse gases.” In 1995, the
Intergovernmental Panel on Climate Change (IPCC) reported that the biosphere has
already warmed about 0.6˚C over the last century and the temperature will increase
another 1.1 to 3.6˚C in the next century due to a discernible human influence on a
global climate. The temperature rise of this magnitude will change local and global
climates, temperatures and precipitation patterns, induce a sea level rise and alter
the distribution of fresh water supplies. The impact on our health by global warming
is likely to be significant.
There are two types of global warming contributions through refrigeration and
air-conditioning systems. The first one is the direct global warming potential
(DGWP) due to the emission of refrigerants and their interaction with heat radiation.
The second is the indirect global warming potential (IDGWP) due to the emission
of CO2 by consuming the energy that is generated through the combustion of fossil
fuels. The combined effect of these two global warming contributions is called the
total equivalent warming impact (TEWI) (Fish et al., 1991).
Introduction 11
TABLE 1.2
HCFCs Regulation Schedule
Jan. 1, 1996 2004 2010 2015 2020 2030
Freeze 35% 65% 90% 99.5% 100%

consumption reduction reduction reduction reduction reduction
The base level is the sum of its 1989 ozone-depletion potential (ODP) weighted HCFCs
consumption plus 3.1% of its 1989 ODP weighted CFCs consumption.
1.5.3 INTERNATIONAL EFFORTS ON ENVIRONMENTAL PROTECTION

Concern over the potential environmental impacts of ozone depletion led to the
development of an international agreement, the Montreal Protocol, to reduce the
production of ozone-depleting substances such as CFCs, hydrochlorofluorocarbons
(HCFCs) and halons. After the Montreal Protocol was signed in 1987, the regulation
was extended in a follow-up conference. At the fourth meeting of the parties to the
Montreal Protocol in November 1992, new controls were required to phase out CFCs
by the end of 1995 and HCFCs by 2030 (Table 1.2; Reed, 1993). Now the regulation
of HCFCs is being tightened with a faster schedule and some countries already have
more severe regulation plans. In the United States, the phaseout of R22 in new
machinery is set for the year 2010 (Allied Signal Chemicals, 1999) and in Germany
it was set for January 1, 2000 (Kruse, 1993).
In 1997, the Parties to the United Nations Framework Convention on Climate
Change agreed to an historic Kyoto Protocol to reduce greenhouse gas emissions
and set emission reduction targets for developed nations: 8% below 1990 emissions
levels for the European Union, 7% for the United States and 6% for Japan. Emission
reduction targets include hydrofluorocarbons (HFCs) that are some of the alternative
refrigerants introduced as a response to ozone depletion.
1.5.4 IMPACT OF ENVIRONMENTAL ISSUES ON U.S. CLIMATE

CONTROL INDUSTRY
The Montreal Protocol and Kyoto Protocol forced the climate control industry to
change refrigerants. In the U.S., the Clean Air Act Amendments of 1990 based on
the Montreal Protocol forced the climate control industry to change its use of CFCs
to HFCs. However, the European Union encourages the use of natural refrigerants
such as hydrocarbons and carbon dioxide. Therefore, the search for the alternative
refrigerants is still wide open but has to be completed in a limited time to satisfy
these two protocols.
1.5.5 MIXTURES AS R22 REPLACEMENTS

R22 is widely used in the air-conditioning and heat pump industry, especially in
residential unitary and air-conditioning systems. The phaseout of R22 requires man-
ufacturers to find suitable alternatives in a relatively short time frame. In 1991, the
Air-conditioning and Refrigeration Institute (ARI) started the R22 Alternative

Refrigerants Evaluation Program (AREP) to find and evaluate promising alternatives
to the refrigerants R22 and R502 for products such as unitary air-conditioners, heat
pumps, chillers, refrigeration equipment and ice-making machines (Godwin, 1993).
This test program involved researchers worldwide and shared experimental results.
Alternative refrigerants were sought to satisfy the following requirements: environ-
mentally benign (zero ODP), nonflammable and similar system level behavior
(equivalent performance, minimum hardware changes). Currently there is no accept-
able pure fluid replacement that satisfies all these requirements. Alternatively, the
mixing of these refrigerants was suggested to fulfill the desired requirements.
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Introduction 15
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Marques, M., S.A. Multibras and P.A. Domanski, 1998, “Potential Coefficient of Performance
Improvements due to Glide Matching with R407C,” Seventh International Refriger-
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McLinden, M.O. and D.A. Didion, 1987, “Quest for alternatives,” ASHRAE Journal, Vol. 29,
No. 12, pp. 32–36, 38, 40 and 42.
McLinden, M.O., 1988, “Thermodynamic Evaluation of Refrigerants in the Vapor Compres-
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No. 3, pp. 134–143.
McLinden, M.O., 1990, “Optimum refrigerants for non-ideal cycles — An analysis employing
corresponding states,” Proceedings of the 1990 USNC-IIR-Purdue Refrigeration Con-
ference and ASHRAE-Purdue CFC Conference, West Lafayette, IN, pp. 69–79.
McLinden, M., S.A. Klein, E.K. Lemmon and A.P. Perkin, 1998, “Thermodynamic and
Transport Properties of Refrigerants and Refrigerant Mixtures,” NIST Database 23:
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ersburg, MD.
Midgley, T., Jr. and A. L. Henne, 1930, “Organic fluorides as refrigerants,” Industrial and
Engineering Chemistry, Vol. 22, pp. 542–545.
Midgley, T., Jr., 1937, “From the periodic table to production,” Industrial and Engineering
Chemistry, Vol. 29, No. 2, pp. 239–244.
Molina, M. J. and F.S. Rowland, 1974, “Stratospheric sink for Chlorofluoromethanes: Chlorine
atom catalyzed destruction of ozone,” Nature, Vol. 249, pp. 810–812.
Morrison, G., 1974, “The shape of the temperature-entropy saturation boundary,” Interna-
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Nagengast, B.A., 1989, “A history of refrigerants,” CFCs: Time of Transition, Atlanta, GA,
American Society of Heating, Refrigerating, and Air-Conditioning Engineers, pp. 3–15.
Nagengast, B.A., 1996, “History of sealed refrigeration systems,” ASHRAE Journal, Vol. 38,
No. 1, S37, S38, S42–S46 and S48.
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2 Properties of
Working Fluids
The performance and efficiency of reversible cycles are independent of the properties
of any working fluids. However, the performance and efficiency of a real machine
are determined to a large degree by the properties of the working fluids. Furthermore,
both the first cost and the operating cost of a heat pump are strongly dependent on
the refrigerant properties.
2.1 THERMODYNAMIC DIAGRAMS OF PURE

AND MIXED REFRIGERANTS
This chapter describes the graphic representations of the properties of pure and
mixed refrigerants. Graphical representations foster the development of a good
intuitive understanding of important characteristics of working fluids while helping
to clarify cycle behavior. Some conventional pure fluids, selected because of their
favorable environmental characteristics, are included here for comparison purposes.
In the following, typical diagrams of fluid properties are discussed. In addition, the
determination of the properties for cycle calculations is explained in detail.
When designing a heat pump, the most important thermodynamic variables to
be considered are: pressure, temperature, mass fraction (for mixtures), enthalpy,
specific volume and entropy. To display all variables, a multidimensional diagram
is required. This is not practical, so several two-dimensional diagrams are commonly
used. These diagrams show any two variables on their axes and display other
variables as sets of curves of constant properties such as isobars and isotherms.
Usually, T-s, ln(P)-h or h-s diagrams are used for design calculations of cycles with
pure fluids. However, when mixtures are used, additional variables and concentra-
tions must be considered. In some cases, this is accomplished by showing the
conventional diagrams for constant concentration. Thus, new versions of the same
diagram must be generated when a different concentration of the same mixture is
of interest. Other diagrams show concentration as the independent variable. These
are uniquely suited to study the characteristics of mixtures.
For the sake of simplicity, the explanation focuses on pure fluids and two-
component (binary) mixtures only. From a thermodynamic point of view, a
two-component mixture possesses one additional degree of freedom as compared to
a pure fluid — the concentration. The concentration of a mixture may be defined
in many different ways including mole fraction, mass fraction and the like. In this
text, the mass fraction is used throughout, defined as
mass of one component [kg]

x= (2.1)
mass of all compponents [kg]
17
This variable includes values in the range 0.0 ≤ x ≤ 1.0, with 0.0 and 1.0 denoting
the respective pure components. The various definitions for variables describing
mixture compositions are discussed in Section 2.2.2.
2.1.1 TEMPERATURE-MASS FRACTION DIAGRAM

We begin with one of the diagrams that is most important for the understanding of
working fluid mixtures, the temperature-mass fraction (T-x) diagram (Figure 2.1.1).
When the liquid and vapor phases of a mixture coexist in equilibrium, the
saturation temperature varies with the mass fraction even though the pressure is
constant. This behavior is in contrast to a pure fluid where Tsat remains constant.
Figure 2.1.1 shows the temperature-mass fraction diagram (T-x diagram) for a
mixture of two components, R134a and R32, at constant pressure of 1.0 MPa. The
mass fraction axis ranges from 0.0 (pure R134a) to 1.0 (pure R32). The area below
the bubble line represents subcooled liquid. The area above the dew line represents
superheated vapor. The area enclosed by the bubble and dew lines is the two-phase
range region. The boiling point for a mixture of mass fraction x is located on the
bubble line at that mass fraction. The bubble line indicates the saturation temperature
at which the first vapor bubble is formed for the specified pressure and mass fraction
when the temperature is raised from the subcooled liquid region to the saturation value.
The boiling points of the pure components TR134a and TR32 are found on the
respective ordinates. According to Figure 2.1.1, the boiling point of R134a is higher
than that of R32. The dew line indicates the temperature at which the first liquid
droplet is formed when a superheated gas mixture of a given mass fraction is cooled
at constant pressure.
50
TR134a Superheated vapor

40
Temperature [°C]
30 Dew line
P = 1 MPa
2-p
has
e ra
ng e
20
10 T R32
Bubble line
Subcooled liquid
0
0.0 0.2 0.4 0.6 0.8 1.0
Pure R134a Mass Fraction of R32 [kg/kg] Pure R32
FIGURE 2.1.1 Temperature-mass fraction diagram for R32/R134a.

Properties of Working Fluids 19
50
Superheated vapor
TR134a
40
Dew line
5"
Temperature [°C]
30
P = 1 MPa
T4 4' 4"
T3 3' 3 3"
20 T2 2"
2-ph
2' ase r
ange
TR32
10 1'
x2' x3' Bubble line
Subcooled liquid
x3" x3'
0 x3" x1,2 x3'
0.0 0.2 0.4 0.6 0.8 1.0
FIGURE 2.1.2 Evaporation process of R32/R134a.
To demonstrate the use of the diagram, a slow (equilibrium) evaporation process

at constant pressure is discussed as an example in Figure 2.1.2. The process begins
with subcooled liquid at point 1′. Points with a single prime denote the liquid phase;
points with a double prime, the vapor phase. As the mixture is heated, the temperature
increases and the bubble line is reached. This is point 2′. Here the first vapor bubble
forms. The mass fraction of the first vapor bubble is found at point 2″. This vapor
is in thermal equilibrium with the liquid phase at point 2′. The vapor is enriched in
R32 as compared to the liquid and has a mass fraction of x2. This is a consequence
of the fact that at the same temperature, R32 has a higher vapor pressure than R134a.
Thus, the vapor phase is bound to contain more R32 molecules.
As the heating process continues, the evaporation process proceeds to point 3,
where the mass fraction of the vapor in equilibrium with the remaining liquid is
represented by point 3″. The mass fraction of the liquid is now indicated by 3′. At
this point, the amount of R32 in the remaining liquid has been reduced as compared
to point 2′ while the vapor is enriched in R32. However, the vapor contains a lower
fraction of R32 and more of R134a than at point 2′. The same is true for the remaining
liquid. As the evaporation process proceeds, the state points of the liquid and vapor
phases continue to follow the bubble and dew point lines. When point 4″ is reached,
the evaporation process is complete. The vapor has the same mass fraction as the
original subcooled liquid and the mass fraction of the last liquid droplet that evapo-
rated is indicated by point 4′. Further heating produces superheated vapor at point 5″.
During the constant pressure evaporation process, the saturation temperature
changed from T2 to T4. The temperature difference (T4 – T2) is termed temperature
glide. Vapor quality xq (defined as the ratio of mass of vapor over total mass) at
point 3 can be calculated based on a mass balance for the mixture and one pure
component. The overall mass balance is given by
m3″ + m3′ = m2′ (2.2)
and the mass balance for one component (here R32)
m3″ x3″ + m3′ x3′ = m2 x2′ (2.3)
After elimination of m3′, the vapor quality is obtained as:
m3′′ ( x2′ − x3′ )

xq = = (2.4)
m2′ ( x3′′ − x3′ )
The vapor quality at state 3 is represented in Figure 2.1.2 by the ratio of the distances
(x3 – x3′)/(x3″ – x3′) and is expressed as a function of mass fractions only. This is a
unique feature of fluid mixtures.
It is noted that generally the temperature glide increases with increasing differ-
ence between the boiling points of the two pure components. Figure 2.1.3a shows
a temperature-mass fraction diagram for a mixture where the difference in boiling
points is relatively small, thus the temperature glide T is relatively small as well.
Figure 2.1.3b shows the temperature-mass fraction diagram of a mixture where the
difference in the boiling points is large. Accordingly, the temperature glide marked
as T is large as well. The size of the temperature glide is also a function of the mass
fraction. For small and large x, the glide is generally smaller than for intermediate
values of x. The mixtures that show the same characteristics as R32/R134a in Figures
2.1.1 through 2.1.3 are traditionally termed nonazeotropic mixtures or, in more recent
literature, zeotropic mixtures. The name implies that in phase equilibrium, the mass
fractions of the vapor and liquid phases are always different.
Some fluids form from azeotropic mixtures, such as a mixture of R12 and R152a,
or a mixture of water and ethanol. For an azeotropic mixture, the mass fractions of
the liquid and vapor phase are identical at a certain pressure and temperature as
shown in Figure 2.1.4. This state is called the azeotropic point and the mass fraction
of this point is called the azeotropic mass fraction. The temperature glide is zero at
this point. At all other mass fractions, the mixture exhibits zeotropic behavior. The
difference in mass fraction between the liquid and vapor phases changes its sign
when the overall mass fraction varies from a value less than the azeotropic mass
fraction to a value larger than the azeotropic mass fraction.
There are unique features of azeotropic mixtures that can make their use bene-
ficial. First, they provide another unique normal boiling point that might not be
covered by one of the pure compound refrigerants and therefore the possibility exists
of fitting some specific application more precisely. Second, they have all of the
benefits of pure compound refrigerants — constant boiling point and heat of vapor-
ization, without the fractionation. Third, they can make up for the physical or
chemical deficiency of one of the zeotropic components, like covering up the flam-
mability of R152a in R500 (Fairchild, 2000).
There are two types of azeotropes, distinguished from one another by the location
of the boiling points at the azeotropic mass fraction relative to the boiling points of
the pure fluids. The boiling point can be either higher than the boiling point of both
Pressure = Constant
Dew line
T Two-phase
range
Boiling
line
x
x
(a)
Pressure = Constant
Dew line
T Two-phase
range
∆T
Boiling
line
∆x
x
(b)
FIGURE 2.1.3 Temperature-mass fraction diagrams with constituents of varying differences

in boiling points.
of the two constituents of the mixture, as in Figure 2.1.4, or lower than the boiling
point of the two constituents, as illustrated in Figure 2.1.5.
Figure 2.1.6 shows the T-x diagram for the azeotrope R507A at a pressure of
0.1 MPa. R507A is a mixture of R125 and R143a with a mass fraction of 0.5 of
R125. Although Figure 2.1.6 shows that the mass fraction of the azeotropic point is
approximately 0.35 of R125 (the maximum in the saturation line), it is also noteworthy
that the temperature glide is very small throughout the entire mass fraction range.
Pressure = const.
Temperature
Azeotropic point
A Mass Fraction B
FIGURE 2.1.4 T-x diagram for zeotropic mixture. (Tsat of the azeotropic point > Tsat of the
pure fluid.)
Pressure = const.
Temperature
Azeotropic point
A Mass Fraction B
FIGURE 2.1.5 T-x diagram for zeotropic mixture. (Tsat of the azeotropic point < Tsat of the
pure fluid.)
This is a consequence of two characteristics: The boiling points of the pure

components are very close and there is not much of an opportunity for the bubble
and dew line to diverge because the two components form an azeotrope. The actual
mass fraction of the azeotropic point is not of much importance for applications in
heat pumps; the fact that the temperature glide is negligible is the important char-
acteristic.
R125/R143a Mixture
−47.0
Superheated vapor
Sat. liquid
Sat. vapor
Dew line
P = 0.1 MPa
−47.5
Temperature [°C]
−48.0 Bubble line
Subcooled liquid
−48.5
0.0 0.2 0.4 0.6 0.8 1.0
FIGURE 2.1.6 T-x diagram for azeotrope R507A (P = 0.1 MPa).
R125/R143a Mixture
17
Superheated vapor Sat. liquid
Dew line
Sat. vapor
16 P = 1 MPa
Temperature [°C]
15
Bubble line
14
Subcooled liquid
13
0.0 0.2 0.4 0.6 0.8 1.0
FIGURE 2.1.7 T-x diagram for azeotrope R507A (P = 1 MPa).
Figure 2.1.7 shows the T-x diagram for R507A at a pressure of 1 MPa. An
inspection and comparison of Figures 2.1.6 and 2.1.7 reveal that the azeotropic point
moves. In this case, the mass fraction of the azeotropic point decreases as the pressure
is increased from 0.1 MPa (Figure 2.1.6) to 1 MPa (Figure 2.1.7) and the azeotropic
point seems to disappear to the left. This is an interesting characteristic of azeotropes.
The azeotropic point changes its mass fraction with the saturation pressure level and
can disappear altogether for certain conditions. A zeotropic mixture may have an
azeotropic point at other conditions and vice versa.
While an azeotropic point is more likely to exist when the boiling points of the
constituents are close together, it is certain to exist when the vapor pressure curves
Psat(T) of the two pure components cross. Such a point usually does not exist when
the boiling points are more than 30 K apart.
2.1.2 PRESSURE-TEMPERATURE DIAGRAM

For preliminary investigations and comparisons of working fluids, the pressure-
temperature diagram (or vapor pressure diagram, as it is often referred to) turns out
to be very helpful. Figure 2.1.8 shows the vapor pressure curves for a number of
pure fluids as examples for past, current or possibly future refrigerants. The lines
suggest an exponential increase of pressure with temperature. Engineers usually
prefer straight lines in diagrams wherever possible. To achieve this, the ordinate is
changed to a logarithmic axis (Figure 2.1.9) and the temperature axis to (–1/T)
(Figure 2.1.10). In this way, the temperature axis becomes nonlinear, the vapor
pressure curves become almost straight lines and the temperature still increases from
left to right. The reason for this selection is given by the Clapeyron’s Equation
described in Section 2.2. This diagram is referred to in this text as the ln(P)-(–1/T)
diagram.
12
3
NH
10
CO2
8
Pressure [MPa]
R32
6
R1 opan22
34 e
Pr R
Bu ane
a
ne
t
bu
23
ta
25
R1
Iso
4
R1
ene
pyl
Pro
2
0
−50 0 50 100 150 200
Temperature [°C]
FIGURE 2.1.8 Vapor pressure curves for a number of pure fluids. The curves end at the
critical points of the respective fluids.

100
5 R22 NH 3
10 CO 2 R12
R32 ane
y le n e Prop4a buta
ne e
Prop R13 Iso Butan
R123
1
Pressure [MPa]
0.1
0.01
0.001
−50 0 50 100 150 200
Temperature [°C]
FIGURE 2.1.9 Vapor pressure curves on a ln(P)-T diagram.
100
2
R2
3
10 NHpane
CO 2 2
R3 Pr o
25
R1
l ene
py
Pro
Pressure [MPa]
0.1
a
34
R1ane
t
bu ne
0.01 Iso uta
B
23
R1
0.001
−5.0 −4.5 −4.0 −3.5 −3.0 −2.5 −2.0
−1/Temperature × 1000 [1/K]
FIGURE 2.1.10 Vapor pressure curves on a ln(P)-(–1/T) diagram. (The lines are almost
straight.)

The advantage of this representation is the fact that the plots of bubble point
temperature versus saturation pressure are almost straight lines for most fluids and
fluid mixtures when the mass fraction is constant. These plots are also referred to
as vapor pressure curves. The following statements are valid for pure fluids only.
The area to the left of the vapor pressure curve of a given fluid represents the
subcooled liquid region. This is the region of higher pressures or lower temperatures
as compared to the saturation values. The area to the right represents superheated
vapor, the region of higher temperatures or lower pressures compared to the satu-
ration values. The two-phase range is represented by the vapor pressure line itself.
In some representations, the vapor pressure curves are drawn exactly as straight
lines. These diagrams were originally developed by Dühring and are now referred
to as Dühring plots.
For fluid mixtures, curves similar to vapor pressure curves can be obtained by
plotting the vapor pressure versus –1/T for the isosteres (lines of constant mass
fraction) of the saturated liquid phase (vapor quality is zero).
Figure 2.1.11 shows an example for R32/R134a. The space between the vapor
pressure curves of the pure constituents of the mixture is termed the solution field.
Pressure-temperature diagrams of mixtures are used extensively for the representa-
tion of cycle configurations in absorption technology.
Azeotropic mixtures yield vapor pressure lines similar to those for pure com-
ponents shown in Figure 2.1.11. However, while in zeotropic mixtures all vapor
pressure curves for mass fractions x with 0.0 < x < 1.0 are located between the lines
for the two pure components, the vapor pressure curve for the azeotropic mass
10
0.2 0. 6
1
n
Pressure [MPa]
ctio
fra
ass
m
34a
R1
0.0
0.1 0.4
0.8
1.0
0.01
−4.5 −4.0 −3.5 −3.0 −2.5
−1/Temperature × 1000 [1/K]
FIGURE 2.1.11 ln(P)-(–1/T) diagram for R32/R134a.

fraction of an azeotropic mixture is located outside the range limited by the vapor
pressure curves of the pure components.
2.1.3 PRESSURE-ENTHALPY DIAGRAM

Figures 2.1.12 through 2.1.24 show examples of pressure-enthalpy (ln(P)-h) dia-
grams for an number of pure fluids and mixtures. This diagram is widely used in
the refrigeration field for the evaluation and design of vapor compression cycles.
The diagram and its various parts are explained next. Figure 2.1.25 shows a
schematic of the diagram for a pure fluid. The ordinate shows the logarithm of the
pressure, the abscissa the specific enthalpy. The two-phase range is found under the
vapor dome, the area where the isotherms are horizontal. To the left of the two-
phase region is the subcooled liquid region and to the right is the superheated vapor
region. The boundary line between the subcooled liquid range and the two-phase
region is the saturated liquid line and the boundary between the superheated vapor
and the two-phase range is the saturated vapor line. The lines of saturated liquid
and saturated vapor converge at the critical point. Above the critical point there is
no distinction between phases, i.e., no meniscus exists. A ln(P)-h diagram shows
several sets of lines of constant properties. Figure 2.1.25 shows only one line as an
example for the various sets. The first discussed here is the isotherm.
The isotherm of this system shows a slight increasing curvature toward the
horizontal (but does not reach a zero slope) as the critical point is approached close
to the saturated liquid line. This gives the subcooled enthalpy of a given temperature
a slightly lower value than that of saturated liquid at pressures closer to the critical
point. R410A is an example where this effect can become significant at higher
pressures. In the two-phase region, the isotherm is a straight horizontal line. This is
a consequence of the fact that pressure and temperature are constant during a phase
change process. In the superheated vapor region, the isotherm curves very quickly
to the vertical and approaches ideal gas behavior (i.e., the enthalpy of an ideal gas
is independent of the pressure). The change in slope of the isotherm at the transition
points between regions is not steady. Above the critical point, the slope of the
isotherm is negative until very high pressures are reached; however, the second
derivative changes its sign in the neighborhood of the critical point. Only at the
critical point itself does the isotherm have a saddle point. This isotherm is sometimes
called the critical isotherm.
The isentrope, the line of constant entropy, is shown frequently in the vapor
phase only where it has a positive slope. In Figure 2.1.25, a single isentrope is shown
as an example. Also indicated is how the isentrope extends into the two-phase range.
There is no abrupt change in the slope of the isentrope at the saturation line. The
isentrope is very important to determine compressor work as shown in the text to
follow.
The isochore, the line of constant volume or density, behaves similarly to the
isentrope but shows a much flatter slope. Isochores are important in determining the
volumetric capacity of the working fluid.

15 3
0
00
0 m
00
500
0
80 70 kg/ 400
120
90
10
11
10 600
300
200
150
R-22
80
4 100
60
70
2 50
40
3
30 kg/m
Density =
1.0
20 20
Pressure (MPa)
15
T = 0°C
10
0.4
7.
−20
-K
kg
5.
0.2
kJ/
1.8
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
2.1
1.9
2.2
2.0
S=
3.
0.1 −40
2.
0.9
1.5
T = 160 °C
200
180
140
120
100
1.0
S = 0.8
80
0.04 −60
60
40
20
0.7
0
−20
−40
vapor
uid
0.5
0.02
d liq
x = 0.5
0.6
0.8
0.3
0.7
0.1
0.2
0.4
0.9
2.3
Saturated
2.4
2.2
rate
S=
Satu
0.01
100 150 200 250 300 350 400 450 500 550 600
Enthalpy (kJ/kg)
FIGURE 2.1.12 Pressure-enthalpy diagram of R22. (Copyright 2004, American Society of Heating, Refrigerating, and
Air-Conditioning Engineers, Inc. Reprinted by permission from ASHRAE 2001 Handbook — Fundamentals.)

20 3
0 0 /m 340 0
55 50 460 420 80 kg
3 30 0
26
220
10 180
150
120 3
R-32 0 kg/m
80 y = 10
Densit
80
4 60 60
50
40
40
2 30
Pressure (MPa)
24
20 20
16
1
12
T = 0°C
10
8
g-K
2
J/k
S = 1.5
1.20
0.96
1.04
1.12
1.60
1.28
1.36
1.44
1.76
1.68
0
8
2
6
6
0
4
4
6
2
4
8k
2.4
2.0
2.3
2.5
2.1
2.0
1.8
1.9
2.2
−20
2.7
2.6
0.4
2.4
5
S=
0.88
4
3.2
S = 0.8
200
180
0.2
T = 100°C
160
140
−40
120
2.4
vapor
80
2
60
quid
.5
40
X=0
20
0.1
0.7
0.2
0.6
0.8
0.9
Saturated
0.4
d li
0.3
1.6
0
0.72
−20
rate
−40
0.1 1.4
Satu
8
1.2
2.8
4
96
3.0
2.8
2.7
S=
2.
0.07
100 160 220 280 340 400 460 520 580 640 700 760
Enthalpy (kJ/kg)

20
g/m 3
1600
00
1500
1550
0
0
00
50
900
50
R-123
00
800 600
0k
140
145
130
10
12
12
11
11
135
10
400
320
240
180
3
/m
4 = 160 kg
Density
160
120
140
80
2 60
120
40
100
1 32
Pressure (MPa)
24
80
T = 60°C
16
0.4 12
8
40
0.2 6
K
kg-
kJ/
0.85
0.90
0.94
0.98
1.02
1.06
1.10
1.14
4
1.18
1.34
1.26
1.22
1.30
1.38
1.62
1.42
1.74
1.82
1.46
1.50
1.78
1.86
1.58
1.66
1.70
8
1.54
1.94
4
1.9
2.0
2.0
2.1
2.1
0
3.2
1.9
0.1
20
S=
2.4
300
320
T = 180°C
280
260
240
uid
220
0
200
1.6
160
140
Liq
120
100
0.04 1.2
80
60
40
r
20
ted
−20
vapo
0.8
ura
Τ = 40°C
rated
Sat
0.02 0.6
.5
0.9
0.3
0.7
0.8
0.4
0.6
X=0
0.1
0.2
Satu
6
2.2
2.2
8
4
0.4
2.1
2.1
S=
0.01
160 200 240 280 320 360 400 440 480 520 560 600 640
Enthalpy (kJ/kg)

10
/m 3
0 0 50
0 400
70 60
0
0
300
0 kg
0
0
80
100
90
110
1400
1300
1500
1600
240 R-125
120
180
4
65
150
55
120
45
96
35
2 72
25
60
3
48 kg/m
Density =
15
1 36
5
30
Pressure (MPa)
−5
24
−15
18
T = 25°C
15
0.4
12
3
9.6 kg/m
−35
S = 0.70 kj/kg-k
-K
7.2
0.2
J/kg
.30
0.80
0.75
0.85
0.90
1.00
0.95
6.0
5
1.40
1.20
1.45
1.50
1.55
1.25
5
1.05
1.10
.60
5
S=1
0
5
0k
0
0.8 1.3
.5 1.1
1.7
1.7
1.8
1.9
1.9
1.6
2.0
1
−45
1.8
4.8
apor
T = 115°C
175
165
or
S=
155
0.7
135
0.1
0.6
0.9
0.4
145
0.2
0.3
X=0
125
−55
vap
ated v
105
3.6
0.1
95
85
75
ted
65
T = 5°C
55
45
3.0
35
25
Satur
−65
ura
15
−5
−15
2.4
−25
Sat
−35
−45
−55
1.8
0
2.0
5
5
1.9
0
2.0
2.1
S=
0.04 1.2
0.03
120 160 200 240 280 320 360 400 440 480 520
Enthalpy (kJ/kg)
FIGURE 2.1.15 Pressure-enthalpy diagram of R125. (Copyright 2004, American Society of Heating, Refrigerating,
and Air-Conditioning Engineers, Inc. Reprinted by permission from ASHRAE 2001 Handbook — Fundamentals.)

20
g/m 3
1500
1400
1300
0
1450
1350
300
0
0 0 400
00
50
600
00
500
125
0
70
0k
80
0
115
0
95
90
85
10
11
10
10
120
3
200 kg/m
Density =
160
120
100
4 90
80
70
R-134a 60
60
50
2
40
40
32
24
1
20
Pressure (MPa)
16
T = 0°C
12
0.4 8
6
−20
0.2 4
g-K
3.2
J/k
0.88
1.12
1.20
1.36
1.44
0.64
0.72
0.80
1.28
1.52
1.60
0.96
1.04
2.08
1.76
1.84
2.00
1.92
1.68
2.32
8
2.40
2.24
6k
2.4
2.4
2.1
0.1
S=
−40
1.6
1.2
320
300
por
280
260
T = 160°C
240
0.04
220
200
d va
0.8
vapor
180
−60
140
120
rate
100
0.6
80
d
60
Satu
Saturate
40
20
0
−20
0.02
−40
X = 0.5
0.4
0.4
0.9
0.8
0.3
0.6
0.2
0.1
0.7
0.3
6
2.5
8
2
4
2.4
2.7
2.6
S=
0.01
100 150 200 250 300 350 400 450 500 550 600 650 700 750
Enthalpy (kJ/kg)
FIGURE 2.1.16 Pressure-enthalpy diagram of R134a. (Copyright 2004, American Society of Heating, Refrigerating, and

100 150 200 250 300 350 400 450 500 550 600
10.
8 20
240
8. 4 5 16 01 .00
01 01 0.00 0.0 0
230
0 0.003
0
0.0 0.0 0.004
0
3
105
011
220
012
0.001
01
0
6. 0.005 0
0.0
0.0
0.0
0.00
0.006
R-404A g
c.p. 80 m/k
4. O e = 0.00
Volum 0.010
60
60
50
0.015
40
50
2.
30
40 0.020
0.00095
0.00085
0.00090
0.00075
0.00080
30
20
0.030
20
10
1. 0.040
Temperature = 50 °C
10
10
40
30
20
0
70
60
0.8 0.050
Temperature = 0°C 0.060
0.6
Pressure (MPa)
−10 0.080
0.4 0.10
−20
0.15
uid
−30
liq
liquid
0.2 0.20
0.5
ted
Temperature = 140°C
200
0.6
0.7
0.9
210
0.1
0.2
0.4
0.8
190
0.3
180
170
160
150
ura
130
120
−40
rated
y=
110
100
Sat
0.30
80
90
70
60
alit
50
40
satu
30
0.1
Qu
20
10
0.40
−10
0
−50
−20
−30
−40
0.08
0.06 0.70
−60
0.04 1.0
-K
−70
kg
1.5
kJ/
.20
0.02 2.0
=2
1.90
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50
1.60
1.65
1.70
1.75
1.80
1.85
2.00
2.10
0
py
1.95
2.15
2.25
5
2.05
2.3
5
2.3
0
0
tro
2.4
2.5
2.4
En
0.01
100 150 200 250 300 350 400 450 500 550 600
Enthalpy (kJ/kg)
FIGURE 2.1.17 Pressure-enthalpy diagram of R404A. (Copyright 2004, American Society of Heating, Refrigerating, and

100 150 200 250 300 350 400 450 500 550 600
10.0
4 6 8
13 001 .001 .001 5
010
8.0
2
00 0. 02
0
80 0011
095
085
0 0
01
22
0. 5 0.0 .0030
090
0
0
0.0
0.0
21
2 0 40
0.00
1
0.00
0
0.
6.0 0.00
0.00
0
0
00 .
0. c.p. 0
20
0
0.005060
0
19
R-407C
70
O 0.0
3 /kg
4.0 080 m
e = 0.0
Volum
60
70 0.010
3.0
50
60
40
0.015
2.0 50
0.020
0.00070
0.00080
30
0.00075
40
20
30 0.030
1.0
10
20 0.040
0.8
Temperature−40 °C
0.050
−60
−50
−10
−30
−20
−70
10
0
0.060
0.6
Pressure (MPa)
Temperature = 0°C
0.080
0.4 −10
0.10
0.3 0.15
−20
uid
0.2 0.20
liq
−30
d
r
vapo
0.1
ate
0.2
0.3
0.30
0.4
tur
0.6
0.5
0.7
0.8
y=
0.9
rated
Sa
0.1 −40 0.40

alit
0.08
Qu
Satu
0.50
0.06 −50
0.70
Temperature = 120°C
180
170
160
150
140
130
.K 100110
90
0.04
80
70
1.0
60
50
−60
40
30
20
10
0.03
−10
−20
0
−30
−40
kg
−50
1.5
kj/
.35
0.02 −70 2.0
=2
py
0.80
tro
5
0.70
0.75
0.85
0.90
0
0.60
0
0.95
0.65
1.00
1.05
1.10
1.15
1.20
0
1.40
1.55
1.60
5
0
1.45
1.50
1.65
5
1.25
1.30
0
0
5
5
1.35
0
0
5
0
2.1
0
2.0
2.2
2.3
2.0
2.4
2.1
2.2
2.5
2.5
2.4
1.7
1.7
1.9
2.6
1.8
1.8
1.9
En
5
2.6
0.01
100 150 200 250 300 350 400 450 500 550 600
Enthalpy (kJ/kg)
FIGURE 2.1.18 Pressure-enthalpy diagram of R407C. (Copyright 2004, American Society of Heating, Refrigerating, and

Enthalpy (kj/kg)
100 150 200 250 300 350 400 450 500 550 600
6 6
4
0.000.005 6 0.008
4 60 0.00 0.010 4
DuPont Fluorochemicals 50
0.015
SUVA 410A ®
Pressure-Enthalpy Diagram
40
0.020
2 30 2
(SI Units)
20 0.030
10 0.040
1 1
0.050
0.8 Temperature = 0°C 0.8
re = 50°C
0.060
180
170
160
150
0.6 0.6
140
130
−10
120
110
100
90
80
70
0.10
Tempe tu60
40
−20
30
0.4 0.4
20
10
ra
−10
0
Pressure (MPa)
Pressure (MPa)
0.15
−30
0.20
0.2 0.2
−40
0.30
0.40
−50
id
g
0.1 0.50 m Y/k 0.1
liqu
0.5 Volume =
0.60
ted
0.08 0.08
ty =
ura
0.80
Quali
0.06 0.06
Sat
1.0
0.04 −70 0.04

1.5
kg-K
2.0
0.02 −80 0.02
j/
3.0
1.8 k
2.2
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.9
2.0
2.1
2.4
2.5
20 2.3
2.6
4.0
py =
0.01 0.01
2.7
2.8
5.0
30
−90
40
Entro
50
6.0
60
0.008 70
80
0.008
0.006 8.0 0.006
100 150 200 250 300 350 400 450 500 550 600
Enthalpy (kJ/kg)
FIGURE 2.1.19 Pressure-enthalpy diagram of R410A. (Chart supplied by DuPont Refrigerants.)

500 3
Ammonia 750 700 650 kg/m 600 550 500
R-717 450
200 400
350
300
100 250 3
0 kg/m
Density = 20
150
40
100
80
20
T= 0
T = 20°C
60
24
440
22
40
20
100
120
−20
180
−60
420
38
−40
36
80
14
160
60
0
34
32
0
28
40
0
0
26
30
40
0°C
0
0
0
0
0
0
10 30
Melting line
20
Pressure (MPa)
15
4.0 10
8
g -K
6
2.0 .0
kJ/k
7.0
S = 5.0
5.5
10.0
.5
6.0
6.5
7.5
8.0
8.5
9.5
4.5
11
9.0
.5
11 4
10
S=
1.0 12
.0 3
2
5
12. 1.5
0.4 1.0
0.8
0.6
0.2
uid
0.4 kg/m3
Vapor
Liq
0.1 0.3
420
T = 220°C
380
340
300
0.2
260
180
d
0.15
140
Saturated
rate
100
0.04
400
60
360
320
Satu
0.10
280
20
−20
240
T = 480°C
200
160
120
440
460
0.02
80
0.1
0.2
X = 0.5
0.3
.0
0.9
0.6
0.8
0.4
.5
0.7
40
13 14
0
.0
−40 13 S=
0.01
−1200 −1000 −800 −600 −400 −200 0 200 400 600 800 1000 1200 1400 1600 1800
Enthalpy (kJ/kg)

100 3
0 g/m 700 600
50
00
50
500
00
90 0k
11
11
10
10
80
400
T=
420
400
380
360
80
200
280
100
340
160
−20
120
20
140
320
300
60
260
40
18
−40
220
240
0
40 300
°C
250
200
Melting line
K
g-
20 150
/k
S = 3.0
kJ
2.8
4.0
3.9
3.8
3.7
4.3
3.4
3.6
4.2
4.5
4.1
4.4
3.2
S=
4.6
100
4.7
10 Carbon dioxide 80
Pressure (MPa)
R-774 60
3
g/m
= 50 k
Density
40
4.0 30
25
20
420
380
2.0
340
300
15
260
T = 220 °C
400
180
360
320
140
280
Saturated vapor
10
240
100
200
d
rate
60
160
8.
1.0
120
20
Satu
5.2
−20
6. kg/m
80
5.1
X = 0.5
40
0.9
0.2
0.3
0.7
0.8
0.1
0.4
0.6
5.0
0
4.9
S=
−40
4.8
4.7
Triple point
0.4
300 400 500 600 700 800 900 1000 1100 1200 1300
Enthalpy (kJ/kg)

70
0 3
m
0
70
0
kg/ 400 300
0
0
65
60
55
35
50
40 450
250
200
Melting line
20 150
70
T = 180 K
68
0
66
320
360
260
280
300
64
220
340
140
160
200
240
0
62
38
40
58
46
T=
42
56
60
44
54
48
100
52
0
0
0
0
0
0
0
0
0
0
0
50
0
10
0K
70
50
PROPANE 40
3
4. R-290 Density=30 kg
/m
20
2. 15
-K
Pressure (MPa)
kg
S= 4.0
kJ/
4.8
4.6
5.0
3.6
5.8
5.2
10
4.4
5.4
5.6
6.0
6.4
7.0
6.2
6.8
7.2
6.6
7.4
1. 7.
S=
7.6
5.
4.
0.4 3.
2.
0.2 1.5
1.0
.5
0.1
0.2
0.6
0.7
0.3
0.8
0.4
d vapor 0.9
X=0
uid
0.1 0.7
d liq
0.5
rate
0.4 kg/m3
Satu
Saturate
380
0.04 0.3
340
300
700
680
660
640
7.6 T=500 K
620
600
580
260
560
540
0.2
520
480
220
460
440
420
0.02
400
360
0
320
8.2
8.
7.8
280
=
240
S
0.01
100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
Enthalpy (kJ/kg)

30
3
m
kg/
0
0
0
45 400 350 300
55
60
50
250
200
10 Normal butane 150
R-600
100
70
420
4.0 50
400
40
30
380
2.0
T = 340 K
360
20
15
Pressure (MPa)
1.0 3
Density = 10 kg/m
320
7.0
0.4 300 5.0

4.0
g-K
3.0
kJ/k
0.2
280
4.4
4.8
5.0
5.2
5.4
5.6
4.2
6.4
6.6
6.0
6.2
2.0
4.6
s = 4.0
5.8
S=
1.5
0.1
uid
r
Vapo
1.0
L iq
260 0.7
0.04
ated
d
0.5
rate
T = 440 K
Satur
420
0.4
Satu
560
580
380
600
540
520
340
500
480
460
300
240 0.3
400
260
360
X = 0.5
0.02 320
0.1
0.3
0.6
0.7
0.8
0.9
0.2
0.4
7.0
280
6.8
240
S=
0.01
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Enthalpy (kJ/kg)

30
3
m
0 kg/
0
250
0
350 300
0
Isobutane 45 400
60
55
50
R-600a 200
10 150
100
70
4.0
400
50
40
380
30
2.0
360
3
Density = 20 kg/m
340
15
Pressure (MPa)
1.0
320
T = 300 K
10
7.0
0.4 5.0
4.0
280
-K
J/kg
3.0
0.2
k
3.8
4.0
5.2
4.8
4.6
4.2
5.0
5.6
4.4
5.4
6.4
5.8
6.0
6.2
2.0
260
s = 3.6
S=
1.5
0.1 3
1.0 kg/m
uid
or 0.7
Liq
ted vap
0.04 240 0.5

0.4
ated
600
580
560
380
540
520
T = 440 K
Satura
340
500
480
460
Satur
0.3
300
420
400
0.02
260
X = 0.5
360
320
6.6
0.1
0.3
0.6
0.7
0.8
0.9
0.2
0.4
280
S=
240
0.01
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Enthalpy (kJ/kg)
FIGURE 2.1.24 Pressure-enthalpy diagram of R600a. (Copyright 2004, American Society of Heating, Refrigerating, and

ln(P)
Isotherm
Critical point
e
op
ntr
I se
Isochore
Subcooled Superheated
liquid vapor region
region
Line of
constant
2-
2-phase range region
(vapor dome) vapor quality
FIGURE 2.1.25 Schematic of ln(P)-h diagram.
ln(P)
hlatent h
FIGURE 2.1.26 Latent heat (∆hlatent) in ln(P)-h diagram.
The ln(P)-h diagram is highly regarded in the refrigeration industry because it

shows very quickly and clearly the amounts of heat exchanged or work required for
the various processes. As long as all processes are steady state or steady flow
processes, the change in enthalpy describes the amount of energy added or extracted.
For example, the latent heat of a fluid for a given saturation pressure is determined
by the enthalpy difference between saturated vapor and saturated liquid. In Figure
2.1.26, the latent heat is indicated. An inspection of Figure 2.1.26 shows that the
latent heat decreases as the pressure increases and reaches the critical pressure. It
should be noted that any difference in enthalpy is related to the addition or extraction
of energy from the fluid, even if the process is not a constant pressure process. This
is discussed in more detail in Section 2.2.

ln(P)
Isotherm
Two-phase region
FIGURE 2.1.27 Various optional shapes for isotherms in the two-phase region of an ln(P)-h
diagram.
At first glance, the pressure-enthalpy diagrams for zeotropic mixtures have the
same general topology as those for pure fluids. However, there are two important
differences (Figure 2.1.18). R407C is chosen here as an example although it is a
ternary mixture. However, the characteristics of multicomponent mixtures and binary
mixtures in the ln(P)-h diagram are the same.
The first difference between the diagrams of pure fluids and mixtures is that the
zeotropic diagram is valid only for a given mass fraction. For a different mass
fraction, all the lines on this diagram shift. Thus, it is only possible to show one
diagram at a time with a full set of lines of constant properties. If one attempted to
superimpose a second diagram for a different mass fraction, the graphical represen-
tation would become incomprehensible. Only one mass fraction is typically circu-
lating in a vapor-compression cycle.
Second, due to the temperature glide in the two-phase region, the isotherms in
the two-phase region have a negative slope. Depending on the nature of the pure
fluids that constitute the mixture, the isotherm in the two-phase region may be
concave, convex, s-shaped or a straight line. The schematic in Figure 2.1.27 shows
examples of these isotherms. When one considers a constant pressure evaporation
process that commences with saturated liquid and ends with saturated vapor, it
becomes apparent that the beginning of the evaporation process starts at a given
isotherm and ends at an isotherm of higher temperature. Thus, the temperature glide
is correctly represented.
2.1.4 TEMPERATURE-ENTROPY DIAGRAM

Temperature-entropy (T-s) diagrams are traditionally used in the design of power gen-
eration plants. The only example for such a diagram that is frequently found in ther-
modynamics texts is the one for water and steam. Here the T-s diagram is shown
primarily to indicate the differences between the one for pure fluids and the one for
mixtures. Figure 2.1.28 shows the schematic of a diagram for a pure fluid. The two-phase

r
Isoba
Critical point
Subcooled
liquid
region Superheated
vapor region
2-
2-phase range region
(vapor dome)
Isenth
Line of a lp
constant
vapor quality
s
FIGURE 2.1.28 T-s diagram for a pure fluid.
range (vapor dome) has a similar shape compared to the mixture diagram. Again, the
subcooled liquid range is located to the lower entropy (left) side of the vapor dome,
the superheated vapor region is to the right of the vapor dome and the lines constituting
the vapor dome are the saturated liquid and saturated vapor lines. They culminate in
the critical point on top of the vapor dome. The isobar is horizontal in the two-phase
region and ascends from the saturated vapor line with increasing slope into the super-
heated vapor region. From the saturated liquid line reaching into the subcooled liquid
region, the isobar drops very quickly and hugs the saturated liquid line, following it
much more closely than shown in Figure 2.1.28, especially when pressures are low.
In a T-s diagram for a zeotropic mixture, all lines are similar to the pure fluid
with the exception of the isobars. To correctly represent the temperature glide, the
isobars must show a positive slope in the two-phase region. Depending on the nature
of the pure fluids that constitute the mixture, the isotherm in the two-phase region
may be concave, convex, s-shaped or a straight line. The schematic in Figure 2.1.29
shows examples of these isotherms.
When considering a constant pressure evaporation process that commences with
saturated liquid and ends with saturated vapor, it becomes apparent that the beginning
of the evaporation process starts at a given temperature and ends at a higher tem-
perature on the same isobar.
2.1.5 TEMPERATURE-ENTHALPY DIAGRAM

Granyrd et al. (1991) suggested using temperature-enthalpy (T-h) diagram for zeo-
tropic mixtures that have a temperature glide during their phase change processes.
Benefits of T-h diagrams include ease of finding cycle problems, such as heat
exchange pinch-points and wet-compression.
Figure 2.1.30 shows T-h diagrams of pure R22 and a zeotropic mixture R22/R114
(50/50 wt.%). Figure 2.1.30 shows different characteristics of isobaric phase change
processes. The isobaric phase change lines have a zero slope for pure R22, but have
nonzero slope for the zeotropic mixture R22/R114 (50/50 wt.%). Nonzero slope

r
Isoba
T
FIGURE 2.1.29 Various possible shapes of isobars in the two-phase range of a T-s diagram
for zeotropic mixtures.
means a finite specific heat in the two-phase range. Moreover, the slope varies with
respect to enthalpy; this means a variable specific heat resulting from a varying latent
heat of vaporization due to the changing liquid and vapor mass fractions of constit-
uents. The superheated region forms a narrow band as compared to other diagrams.
When the refrigeration cycle is superimposed together with temperature profiles
of secondary fluid heat source and sink on the T-h diagram, the benefit of zeotropic
mixtures is demonstrated graphically. Figure 2.1.31 shows the T-h diagram of a cycle
with heat exchange operating 400 kPa evaporation and 1600 kPa condensing pres-
sures for pure R22 and the zeotropic mixture R22/R114 (50/50 wt.%). In Figure
2.1.31, the cycle ABCD represents the refrigeration cycle (A–B: evaporation, B–C:
compression, C–D: condensation, D–A: isenthalpic expansion) and the lines Ae–Be
and Cc–Dc represent temperature profiles of heat source and heat sink. When the
temperature difference between the refrigerant and secondary fluid are compared
for two refrigerants, as shown in Figure 2.1.31, advantages of zeotropic mixtures
become distinct. For R22, the saturated vapor temperature during its condensing
process is closest to the secondary fluid temperature, showing a potential heat
exchange pinch-point. Moreover, R22 shows nonuniform approach temperatures
during its evaporation process, whereas R22/R114 shows almost uniform and smaller
approach temperatures than those of R22 during its evaporation and condensation
processes. Therefore, approach temperatures at the inlet and outlet of both R22 heat
exchangers are larger than those of R22/R114. Large approach temperatures mean
higher irreversible losses associated with heat exchange. Therefore zeotropic mix-
tures having temperature glides that are properly matched with the secondary fluids
have less irreversible losses than those of pure refrigerants.
2.1.6 PRESSURE-MASS FRACTION DIAGRAM

It should be noted that some designers prefer the pressure-mass fraction (P-x)
diagram to the temperature-mass fraction diagram that was discussed in detail at the

(a) (b)
150 150
constant pressure constant pressure

constant entropy constant entropy
100 100
a
saturation 2600 kP
Temperature (°C)
Temperature (°C)
2600 kPa a
incr 1600 kP
50 1600 kPa entr easing 50 1200 kPa
opy
saturation
1200 kPa 800 kPa
800 kPa
400 kPa
0 400 kPa 0
200 kPa
200 kPa
100 kPa
100 kPa
−50 −50
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Enthalpy (kJ/kg) Enthalpy (kJ/kg)
FIGURE 2.1.30 Temperature-enthalpy diagram (Granyrd et al., 1991). (a) R22, (b) R22/R114 (50/50 wt.%).

150 150
100 100
C
Temperature (°C)
Temperature (°C)
1600 kPa
Cc
50 1600 kPa 50 D
D Cc Bc
Dc
Dc Bc B
Ac 0 Ac 400 kPa
0 A
A 400 kPa B
−50 −50
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Enthalpy (kJ/kg) Enthalpy (kJ/kg)
(a) (b)
FIGURE 2.1.31 Temperature-enthalpy diagram of cycle with heat exchange (Granyrd et al., 1991). (a) R22, (b) R22/R114 (50/50 wt. %)

Temperature = Constant
Bubble line
Pressure
Subcooled liquid
Two-phase range
Superheated vapor
Dew line
Pure Pure
Fluid A Fluid B
Mass Fraction of B
FIGURE 2.1.32 Pressure-mass fraction diagram.
beginning of this chapter. In principle, both diagrams are very similar except for the
important difference that the general outline is reversed.
Figure 2.1.32 shows a schematic of a P-x diagram. The subcooled liquid region
is now located above the two-phase region and the superheated vapor region is below.
Thus, all processes shown in the diagram are reversed compared to the T-x diagram.
Because this reversal can be quite confusing, it is recommended that readers pick
either the temperature-mass fraction diagram or the pressure-mass fraction diagram
as their favorite representation of mixture properties and then remain consistent. In
this text, the temperature-mass fraction diagram is used exclusively.
2.2 ANALYTICAL TREATMENT OF

THERMODYNAMIC PROPERTIES
This chapter focuses on the thermodynamic relationship between variables and their
mathematical formulation.
2.2.1 TYPES OF SUBSTANCES IN INTERNAL EQUILIBRIUM

Substances in internal equilibrium can be divided into homogeneous and heteroge-
neous categories. A single-component substance is homogeneous when thermophysical
properties are uniform for any arbitrary part of the substance. For single-component
substances, single-phase substances are homogeneous and multiphase substances
are heterogeneous. Combining pure substances forms a mixture. A mixture is homo-
geneous when the composition and thermophysical properties are uniform for any
arbitrary small element of the mixture. When a mixture does not satisfy the conditions

for the homogeneous mixture, it is called a heterogeneous mixture. For multicom-

ponent substances, gas mixtures in thermodynamic equilibrium are homogeneous
mixtures and multiphase mixtures are heterogeneous mixtures. Another difference
between the homogeneous mixture and heterogeneous mixture is that simple
mechanical means (such as gravity, centrifuging or filtration) can separate the het-
erogeneous mixture into its original mixing components, but cannot separate the
homogeneous mixture.
2.2.2 DEFINITIONS OF CONCENTRATION

The following definitions are used in this text: concentration describes the relative
amount of a given component within a mixture. The term composition refers to the
components that make up a mixture. Thus, a mixture of the same composition can
have many different concentrations. In this section, six different types of concentra-
tion used in mechanical and chemical engineering are explained using binary mix-
tures as an example, specifically mass fraction, mole fraction, mass component ratio,
mole component ratio, mass concentration and mole concentration.
Let us assume two pure substances, A and B, form a binary mixture. We define
M, m, mi and V to represent the molecular mass, total mass, component mass and
total volume, respectively. The six different types of concentration are defined as
shown in Table 2.1. These concentrations are related to each other, so if one type
of concentration is given, the other types of concentration can be calculated accord-
ing to Table 2.2. In this text the mass fraction is used predominantly to describe a
mixture concentration.
2.2.3 SOLUBILITY
Solubility is defined as the amount of a substance that dissolves in a specific amount
of the dissolving agent. Two other terms that can describe the solubility are miscible
and immiscible. Two gases form a homogeneous mixture when they are mixed.
Similarly, many liquids, when suitable, are mixed and form a homogeneous mixture;
these fluid pairs are miscible. Liquids that form an inhomogeneous mixture and do
not dissolve are termed immiscible. Substances with the same polarity tend to be
miscible and substances with opposite polarity tend to be immiscible. Good examples
of miscible and immiscible refrigerant mixtures and lubricant pairs are shown in
Table 2.3.
The miscibility depends on the substances that are mixed, the mass fraction and
temperature. Figure 2.2.1 shows the miscibility of refrigerant R134a in a specific
polyol-ester lubricant. The top of the curve point C indicates the minimum temper-
ature at which the refrigerant and lubricant are miscible in all mass fractions. In the
area to the left of the curve, the mixture is refrigerant rich and miscible, while in
the area right of the curve, the mixture is lubricant rich and miscible. In the area
below the curve the refrigerant and lubricant are present in two liquid phases. Each
phase is a homogeneous mixture of refrigerant and oil but of different mass fractions.
The area enclosed by the curve through A, B and C is termed the mixing gap. Their

TABLE 2.1
Types of Concentration for Binary Mixtures
Types of
Concentration Definition Physical Meaning
Mass fraction Mass fraction of material B in the mixture 1 kg of mixture contains x kg

(kg/kg) mB mB of material B and (1 – x) kg
x= = of material A
mA + mB m
Mole fraction Mole fraction of material B in the mixture 1 mol of mixture contains
(mol/mol) ψ mol of material B and
mB M B
Ψ= (1 – ψ) mol of material A
mA M A + mB M B
Mass ratio of Mass concentration of material B Amount of material B for
components mB 1 kg of material A
β=
mA
Mole ratio of Mole concentration of material B Molar quantity of material B
components in the (1 + χ) mol of the
mB M B
χ= mixture as compared to that
mA M A of material A
Mass concentration Mass concentration of material B Amount of material B in
mB 1 m3 of the mixture
c=
V
Mole concentration Mole concentration of material B Molar quantity of material B
in 1 m3 of the mixture
mB M B
cm =
V
Note: M, m and V stand for the molecular mass, mass and volume, respectively.
mass fractions of two liquid phases are given for a certain temperature by the
horizontal limits of the curve for example points A and B at –60˚C. Thus, at –60˚C,
R134a and polyol-ester lubricant are miscible when the lubricant mass fraction is
either less than 4%, point A, or higher than 54%, point B. However, they are not
miscible when the lubricant mass fraction is between the mass fractions of points
A and B.
2.2.4 LIQUID MIXING PHENOMENA

When two liquids are mixed adiabatically, the mass is conserved but the volume
and temperature are usually not. These phenomena are so-called mixing phenomena
and can be explained with the help of Figures 2.2.2 and 2.2.3. When mA kg of liquid
A with a specific volume vA and mB kg of liquid B with a specific volume vB form
mM kg of mixture, the mass, volume, enthalpy and entropy of the liquids before
(index 1) and after (index 2) mixing are as follows:

TABLE 2.2
Transformation of Conentrations for Binary Mixtures
Given Desired Concentration (see Table 2.1 for definitions)

Concentration X Ψ β χ c cm
x
mB x M Ax ρx
x= x MB ρx
m A + mB (1 − x ) + x 1− x M B (1 − x ) MB
MA
Ψ ρΨ
mB M B M BΨ Ψ ρΨ
Ψ= MA Ψ MA
m A M A + mB M B (1 − Ψ ) + Ψ M A (1 − Ψ ) 1− Ψ (1 − Ψ ) + Ψ M A (1 − Ψ ) + M B Ψ
MB MB
β
mB β
β
M Aβ ρβ ρβ M B
β= MB
mA 1+ β +β MB 1+ β 1+ β
MA
χ ρχ ρχ M B
mB M B χ M Bχ
χ= MA χ MA MA
mA M A +χ 1+ χ MA +χ +χ
MB MB MB
mB M Ac c M Aυc c
c= υc c
V ρM B + ( M A − M B )c ρ−c M B (1 − υc) MB
mB M B M Acm M B cm M Acm
c = MBVCm MBcm cm
m V ρ + ( M A − M B ) cm ρ − M B cm ρ − M B cm
υ = specific volume of the mixture; ρ = density of the mixture.

Source: Bosnjakovic, 1965.

TABLE 2.3
Solubility of Refrigerant and Lubricant
Refrigerant Lubricant Solubility
R22 (nonpolar) Mineral oil (nonpolar) Miscible

R134a (polar) Polyol-ester oil (polar) Miscible
R134a (polar) Mineral oil (nonpolar) Immiscible
80
60
40
Temperature [°C]
20
0
Homogeneous Mixture
−20 C
−40
A B
−60
Heterogeneous Mixture
−80
0 10 20 30 40 50 60 70 80 90 100
Lubricant Concentration [wt.%]
FIGURE 2.2.1 Miscibility of polyol-ester lubricant in R134a.
Liquid A Liquid B Mixture = Liquid A + Liquid B

dV
T1 T1 T2 = T1
mA kg m B kg mM kg
vA vB v 2 = ( v A+ v B)
(a) (b)
FIGURE 2.2.2 Liquid mixing phenomena. (a) Two liquids in one container, not mixed. (b)
Liquids are mixed. The total volume is reduced in this example.
Before mixing:
m1 = m A + m B = m M (2.5)
v1 = V1 m1 = (m AvA + mB vB ) mM (2.6)
h1 = (m AhA + m B hB ) m M (2.7)

150
Volume change [mm3/mol] 100 n-Hexane
50
Methyl cyclopentane
0
3-Methyl pentane
−50 2-Methyl pentane
−100
2,3-Dimethyl butane
−150
0.0 0.2 0.4 0 .6 0.8 1 .0
Mass Fraction [kg/kg]
FIGURE 2.2.3 Volume changes at 25˚C for liquid mixtures (Cyclohexane with some other
C6 hydrocarbons). (Perry et al., 1997.)
s1 = (m As A + mB s B ) mM (2.8)
After mixing:
m2 = m1 = 1 (for the sake of simplicity, the total mass is set to 1 kg) (2.9)
v2 ≠ v1 (2.10)
h2 ≠ h1 (2.11)
s2 ≠ s1 (2.12)
The volume change in the mixing of liquids can be measured easily and is
usually small. Figure 2.2.3 shows the volume changes of liquid mixtures, cyclohex-
ane with some other C6 hydrocarbons, at 25˚C. As shown in Figure 2.2.3, the changes
of volume can be either positive or negative depending on the individual mixtures
that are sensitive to the effects of molecular size and shape and to the differences
in the nature and magnitude of intermolecular forces.
In general, the temperature of a mixture is different from the initial temperature
of its components when the mixing process is adiabatic. During the mixing process,
the mixture either rejects or absorbs energy called heat of mixing. When the heat of
mixing is positive, the temperature of the mixture decreases. On the other hand,
when the heat of mixing is negative, the temperature of the mixture increases. Figure
2.2.4 shows the heat of mixing for the H2O/NH3 mixture at 2 MPa and 40˚C. The

250
200
h1 h NH3
hH2O
150
Enthalpy [kJ/kg]
Heat of mixing
100
50
−50 h2
−100
0.0 0.2 0.4 0.6 0.8 1.0
Mass Fraction of NH3 [kg/kg]
FIGURE 2.2.4 Heat of mixing in liquid mixture (H2O/NH3 mixture at 2 MPa, 40˚C).
heat of mixing for the given mixture changes depending on the temperature and
pressure. The heat of mixing for the refrigerants that are the focus of this text is
quite small.
2.2.5 ADIABATIC MIXING OF BINARY MIXTURES

In this section, the adiabatic mixing process will be analyzed as shown in Figure
2.2.5. In Figure 2.2.5(a), two streams of binary mixtures, m A of mixture A and m B
Mixture A Mixture B
mA kg/s mB kg/s
hB
TA, hA, vA, xA TB, hB, vB, xB mM
mA
Enthalpy
Mixing
mB hM
Mixture M
hA
mM kg/s
TM, hM, vM, xM
0 xA xM xB 1.0
Mass Fraction
(a) Mixing of Two Mixtures (b) Mixing Rule
FIGURE 2.2.5 Adiabatic mixing of two binary mixtures.

of mixture B, are mixed adiabatically and form m M of the product mixture stream.
From the mass and energy balances, three conservation equations result:
Conservation of total mass:
m M = m A + m B (2.13)
Conservation of species:
m M x M = m A x A + m B x B = m M x A + m B ( x B − x A ) (2.14)
Conservation of energy:
m M hM = m AhA + m B hB = m M hA + m B (hB − hA ) (2.15)
From Equations 2.13, 2.14 and 2.15, the ratio m A /m B can be expressed in terms
of mass fractions or enthalpies as shown in Equation 2.16,
m A x B − x M hB − hM
= = (2.16)
m B x M − x A hM − hA
The mass fraction (xM) and enthalpy (hM) of the mixture after mixing can be re-
expressed as Equations 2.17 and 2.18 by using the ratio m B /m M ,
m B
xM = xA + (xB − x A ) (2.17)
m M
m B
hM = hA + ( hB − h A ) (2.18)
m M
As Equations 2.17 and 2.18 show, the mass fraction (xM) and enthalpy (hM) of the
product mixture after mixing are a linear function of the two mixtures A and B and
can be obtained by interpolation as shown in Figure 2.2.5(b). In an enthalpy-mass
fraction diagram, Equations 2.17 and 2.18 describe the so-called mixing rule.
Similarly, the temperature of the product stream can be found from the enthalpy
(h) and mass fraction (x) chart as shown in Figure 2.2.6. For example, two streams
of saturated liquid R32/R134a, stream state A at m = 2/3 kg/s, x = 0.11 kg/kg, T =
30˚C, and stream state B at m = 1/3 kg/s, x = 0.75 kg/kg, T = 10˚C, are adiabatically
mixed with each other. The state of mixture M can then be found from the mixing
rule. The mass fraction and enthalpy of M can be calculated from Equations 2.14
and 2.15.

600
P = Const. (1 MPa)
500
t line
Dewpoin
MV
Enthalpy [kJ/kg]
400
30°C 20°C 10°C
300
A Boiling point line
M
B
ML
200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mass Fraction of R32 [kg/kg]
FIGURE 2.2.6 Enthalpy-mass fraction diagram of R32/R134a mixtures.
m B
xM = xA + ( x B − x A ) = 0.11 + 1/3(0.75 − 0.11) = 0.3223 [kg/kg]
m M
m B
hM = hA + (hB − hA ) = 218.0 + 1/3(244.1 − 218.0) = 226.7 [kJ/kg]
m M
The state of M can also be obtained from the h-x diagram by interpolation as shown
in Figure 2.2.5(b). In Figure 2.2.6, states A and B are connected by a straight line.
Then the state point M of the product stream is found at the location where the line
AB is divided in the ratio of AM:MB = 1:2. The temperature of the state point M
is found from the isotherm TM that passes through point M. As can be seen in Figure
2.2.6, the state point M is above the saturated liquid line. Therefore, the state M is
in the two-phase region.
2.2.6 ISOTHERMAL MIXING OF BINARY MIXTURES

When the temperature of the mixture is maintained before and after the mixing
process, the process is called isothermal mixing. To be an isothermal mixing process,
the mixture needs to be heated or cooled to maintain the initial temperature. The
heat of mixing (∆h) for the isobaric and adiabatic process is obtained from the
enthalpy difference between the enthalpies before (h1) and after (h2) mixing as
follows:
Before mixing:
h1 = (m AhA + m B hB ) m M (2.19)

After mixing:
h2 = h1 + ∆h (2.20)
Heat of mixing:
∆h = h2 − h1 = h2 − (m AhA + m BhB ) m M (2.21)
2.2.7 MIXING OF BINARY MIXTURES WITH HEAT EXCHANGE

If heat exchange occurs during the mixing of two binary mixtures, the final state is
affected by the amount of heat removed or added. If the heat q is removed while
mixing, then three conservation equations apply: two conservation equations for
total mass and one species (the same as Equations 2.14 and 2.15) and the energy
equation, Equation 2.22.
Conservation of energy: m AhA + m B hB = m M hM + q (2.22)
Then the enthalpy of the mixture (hM) becomes as Equation 2.23,
m AhA + m B hB − q m (h − hA ) − q
hM = = hA + B B (2.23)

mM m M
When the initial temperatures of the two mixtures are the same before mixing and
maintained constant during the mixing process, the process is called isothermal. To
be an isothermal mixing process, the mixture needs to be heated or cooled to maintain
the initial temperature.
2.2.8 SPECIFIC HEAT OF BINARY MIXTURES

The enthalpy of a binary mixture can be defined using the heat of mixing (∆h) and
the enthalpies of the individual components as follows:
m AhA + m B hB
h = ∆h + = ∆h + (1 − x ) hA + xhB (2.24)
m M
The specific heat of the binary mixture can then be obtained by taking the derivative
of enthalpy with respect to the temperature,
 ∂h   ∂∆h   ∂h   ∂h 
cp =  = + (1 − x )  A  + x  B  (2.25)
 ∂T  P ,x  ∂T  P ,x  ∂T  P ,x  ∂T  P ,x

From the definition of the specific heat of the individual components, Equation 2.25
becomes
 ∂∆h 
cp =  + (1 − x ) c p, A + xc p,B (2.26)
 ∂T  P ,x
As indicated in Equation 2.26, the specific heat of binary mixture is obtained by

summing up the mass fraction weighted specific heat of individual components and
the change of the heat of mixing with temperature.
2.2.9 LATENT HEAT OF BINARY MIXTURES

The phase change of binary mixtures is an important engineering concern because
the vaporization and liquefaction of binary mixtures are used in vapor compression
heat pumps and are much different than those of pure substances. The latent heat
for the phase change of a binary mixture can be defined as the enthalpy difference
of saturated vapor (point MV) and saturated liquid (point ML) at constant pressure
as shown in Figure 2.2.7. Figure 2.2.7 shows the enthalpy-mass fraction (h-x)
diagram of the R32/R134a mixture at 1 MPa pressure. The differences between the
saturated vapor enthalpy and saturated liquid enthalpy at the first and second y-axis
represent the latent heat of evaporation of the pure R134a and R32, respectively. As
an example, from the h-x diagram of R32/R134a, the saturated liquid and saturated
vapor points (points ML and MV) at 0.5 kg/kg mass fraction of R32 can be found
600
P = Const. (1 MPa)
500
Dewpoint line MV
Enthalpy [kJ/kg]
Latent heat (x = 0.5)
Latent heat (R32)

Latent heat (R134a)
400
20.3°C 15°C
300
Boiling point line

ML
200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mass Fraction of R32 [kg/kg]
FIGURE 2.2.7 Enthalpy-mass fraction diagram of R32/R134a mixture at 1 MPa.

from the intersection of the vertical mass fraction line and the saturated liquid and
vapor lines. The saturated liquid enthalpy is then 225.5 kJ/kg at 15˚C and the
saturated vapor enthalpy is 466.2 kJ/kg at 20.3˚C. Therefore, the latent heat of the
R32/R134a mixture at 1 MPa is 240.7 kJ/kg. In this way, the latent heat of the binary
mixture at different pressures and concentrations can be obtained from the h-x
diagram.
2.2.10 CRITICAL POINT OF BINARY MIXTURES

The critical point of pure substances is defined as the high pressure and temperature
endpoint of the vapor pressure curve. Above the critical point (above the critical
pressure and temperature), no liquefaction will take place. Moreover, the critical
point is defined as a state where the saturation liquid and vapor states become the
same as the pressure increases. The critical point is an inflection point where the
curvature of the isobar in the P-V plane changes from positive to negative. The first
and second derivatives of a curve at an inflection point are both zeros. Therefore,
the first and second partial derivatives of the pressure with respect to volume at a
constant temperature Tc are both zero at the critical point as shown in Equations 2.27
and 2.28,
 ∂P 
 ∂V  =0 (2.27)
T =T
c
 ∂2 P 
 ∂V 2  =0 (2.28)
  T =T
c
However, the mixtures have different characteristics than pure substances. The
critical point of mixtures is not the inflection point. Critical point, critical temperature
and critical pressure of mixtures are all different. The critical point of mixtures is
defined as the point at which the dew line and bubble line meet. Figure 2.2.8 shows
the critical envelope of the binary mixture in the pressure-mass fraction diagram.
PCA and PCB represent the critical points of substances A and B, respectively. Critical
envelopes of maximum pressure and temperature are formed while connecting the
two critical points, PCA and PCB. When the pressure of a binary mixture is lower
than the critical pressure of either two substances, the dew and bubble lines at the
same temperature meet at the mass fractions of zero and one. This is the case for
temperatures T1 and T2 in Figure 2.2.8. When the pressure of a binary mixture is
between critical pressures of the two pure substances, the dew line and bubble lines
at the same temperature meet at the mass fraction of zero and less than one. For the
temperature T4, the dew and bubble lines meet at the mass fraction of 0 and x4
(Figure 2.2.8). The liquid and vapor phases at the same temperature and pressure
have the same mass fraction x4 at the critical point CP4. If the temperature is slightly
increased from point CP4, while the mass fraction and pressure are maintained such
that the temperature of the new critical point does not cross the critical envelope of
Critic
PC,A al En
velop
Critica e
l Enve P4,c Supercritical
lope
region
CP4
T4 T4,c
T4 P3,c CP
p ,m
P4,A CP3 ax
T3 T3,cCPt,ma
x
T3 PC,B
Pressure
P2,B
P3,A st.
= con
for T
2
Line st.
Dew T 2 = con
e for
le Lin
Bubb P1,B
P2,A
onst.
T1 = c
ine for onst.
Dew
L 1=c
ine for T
le L
Bubb
P1,A
0 x4 1.0
A Mass Fraction B
FIGURE 2.2.8 Critical envelope of binary mixture in pressure-mass fraction diagram

(Bosnjakovic, 1965).
maximum pressure, the mixture is still in the two-phase region and not in the
supercritical region. Therefore, the state of a mixture can be changed from the
subcritical region to the supercritical region only when the pressure and temperature
increase substantially such that the state point crosses the critical envelope of max-
imum pressure.
It should be noted that the condition where the second and third derivatives of
molar Gibbs free energy with respect to the mixture composition are both zero is
used in the REFPROP as the thermodynamic criteria for the critical loci of binary
mixtures. Pseudocritical parameters are then fitted to empirical functions from the
iteratively calculated critical loci (McLinden, 1998).
2.3 TERNARY AND MULTICOMPONENT MIXTURES

This text deals predominantly with binary mixtures (mixtures composed of two
constituents). However, some of the preferred refrigerant mixtures under consider-
ation are ternary mixtures (composed of three constituents). Table 2.4 shows a listing
of these mixtures. The key thermodynamic characteristics that dominate the perfor-
mance as refrigerants are not different from binary fluid mixtures. There is still a
glide to contend with and that is the most prominent influence. However, the evalu-
ation of thermodynamic properties and the representation of thermodynamic diagrams
become considerably more complex.
2.3.1 THERMODYNAMIC DIAGRAMS FOR

MULTICOMPONENT MIXTURES
The state of a pure fluid can be described with two independent variables, for
example, pressure and temperature. To describe a binary mixture, an additional
variable has to be introduced that describes the concentration. In this text, the mass
fraction was selected. For a mixture with n constituents, we need n – 1 mass fractions
to fully describe all concentrations. The mass fraction of the ith component is defined
as follows,
xi = mi / Σmj with j ranging from 1 to n, and 1 ≤ i ≤ n
It is a considerable challenge to represent the thermodynamic properties of

multicomponent mixtures on thermodynamic diagrams. If the mass fractions are
chosen as some of the axes, multidimensional diagrams result that are hard to display
on a two-dimensional surface. The most commonly used compromise is to show the
conventional diagrams for pure fluids and to keep all mass fractions constant. Figure
2.1.18, the pressure-enthalpy diagram for R407C, is one example.
Ternary mixtures are an exception. A commonly used diagram exists that shows
all three mass fractions on the three axes of a triangular diagram. The fourth axis,
extending out of the surface, shows the property under consideration. Instead of
displaying the fourth axis, its variable is often shown as a set of parametric curves
superimposed on the surface of the triangle; Figure 2.3.1 displays examples of such
a diagram. The corners of the triangle represent the constituents of the mixture. Each
side of the triangle displays the binary mass fraction of the mixture composed of
the constituents of the respective endpoints. Thus, each side has the same meaning
as the x-axis used in the binary mixture diagrams in the earlier parts of Chapter 2,
such as the temperature-mass fraction diagram. A point located on an axis of a
triangular diagram describes the mass fraction of the respective binary mixture, as
is the case for the point marked R410A in Figure 2.3.1(a). A point located somewhere
within the triangle describes a ternary mixture, as with R407C in Figure 2.3.1(a).
R32 R143a
66% flammable
60% 25°C 58% flammable
55%
100 60°C
R410A °C 51.5% R507A
R404A 10
0°C 36%
33% 33%
R407C
nonflammable
nonflammable
R125 R134a R125 R134a
(a) (b)
FIGURE 2.3.1 Flammability diagram for two ternary mixtures. (a) R407C. (b) R404A.
The application of ternary or multicomponent mixtures comes with the same

challenges as that of binary mixtures. The major effects are caused by the temperature
glide; thus, all the considerations in the following chapters hold accordingly. Only
the mass balances must be extended to include additional equations to properly
account for the additional components.
There are no known azeotropes among mixtures with more than two constituents.
2.3.2 FLAMMABILITY OF MIXTURES

The particular purpose of the triangular diagrams of Figure 2.3.1 is to describe the
flammability of the mixtures as a function of mass fraction. In this case, the fourth
axis is flammability and since the only information we are interested in is the
isotherms that limit the regions in which the mixture is flammable or not are shown
in Figure 2.3.1. Flammability depends on the temperature of the mixture (and other
variables such as humidity not considered here) and therefore Figure 2.3.1(a) shows
two isotherms for 25˚C and 100˚C and Figure 2.3.1(b) for 60˚C and 100˚C (UL,
1994).
Figure 2.3.1 also reveals that the fluids R32 and R143a are flammable and R125,
R134a, R407C, R404A, R410A and R507A are not. Table 2.4 summarizes the
properties of the pure fluids including flammability limits in air.
2.3.3 REASONING FOR SELECTING CERTAIN MIXTURES

There are a number of drivers that lead to the selection of certain mixtures. The
overall intent is to develop an ideal refrigerant; that is, one that satisfies all the
demands listed in Chapter 1, such as local and global safety (fluids should be non-
toxic, nonflammable and have no adverse environmental impact) and should perform
TABLE 2.4
Thermophysical Properties of Pure Refrigerants
Property R32 R125 R134a R143a
Chemical formula CH2F2 CHF2CF3 CH2FCF3 CF3CH3
Critical temperature [˚C] 78.1 66.2 101.1 72.9
Latent heata [kJ/kg] 299.0 124.7 190.7 177.7
Specific heata [kJ/kg*K] 1.806/1.367 1.310/0.958 1.370/0.946 1.551/1.164
(liquid/vapor)
LFL to HFLb [%] 12.7 ~ 33.5 None None 7.1 ~ 16.1c
Molecular weight [kg/kmol] 52.0 120.0 102.0 84.0
Thermal conductivitya 0.147/0.0129 0.0663/0.0136 0.0876/0.0124 0.0765/0.0144
[W/m*K] (liquid/vapor)
Note: NIST REFPROP V6.0 (McLinden et al., 1998) unless otherwise noted.
a at 10˚C.
b Richard and Shankland (1992).
c Atofina Chemical (1999).
TABLE 2.5
Environmental and Thermophysical Properties of Binary and Ternary Mixtures
Property R410A R507A R407C R404A
Components R32/125 R125/143a R32/125/134a R125/143a/134a
(50/50 wt.%) (50/50 wt.%) (23/25/52 wt.%) (44/52/4 wt.%)
ODP (R11 = 1.0) 0 0 0 0
GWP (CO2 = 1.0) 1890d HGWP 1.0d 1370b 3260c
Critical temperature [˚C] 70.2 70.8 86.1 72.1
Latent heata [kJ/kg] 208.4 152.2 199.2 156.0
Specific heata [kJ/kg*K] 1.565/1.207 1.427/1.057 1.449/1.009 1.434/1.057
(liquid/vapor)
Molecular weight [kg/kmol] 72.6 98.9 86.2 97.6
Thermal conductivitya 0.108/0.0129 0.0726/0.0141 0.0956/0.0121 0.0731/0.0140
[W/m*K] (liquid/vapor)
Note: NIST REFPROP V6.0 (McLinden et al., 1998) unless otherwise noted.
a At 10˚C.
b Calm (1995).
c Siva and Gustavo (1999).
d DuPont Fluorochemicals (2000).
well in heat pumps for all applications. Table 2.5 summarizes the environmental and
thermophysical properties of the selected binary and ternary mixtures as most prom-
ising alternatives of R22 and R502. Moreover, constituents of these mixtures are
two or three of R32, R125, R134a and R143a.
The properties of the new refrigerants should resemble as close as possible those
of the fluids being replaced. In particular, for R22 no such candidate has been found.
However, based on previous investigations that led to the introduction of R22, it was
known that R32 is the most desirable fluid. It has the highest efficiency of the pure
alternatives to R22 and, because of its high-pressure levels, also a very high volu-
metric capacity. Its only major shortcomings are its moderate flammability, the high
compressor discharge temperature (a consequence of R32’s low specific heat capac-
ity) and the high-pressure levels. The latter can be seen as an asset or challenge,
depending on the point of view.
The refrigerant mixtures R410A and R407C are compromises that aim at main-
taining the favorable characteristics of R32, especially its high efficiency, while
eliminating its shortcomings. R407C aims at achieving a fluid with properties resem-
bling R22 as closely as possible, the only major difference being that R407C has a
temperature glide. R410A, however, has almost no glide and it maintains the very
high-pressure levels of R32.
R410A consists of R32/R125, 50/50 wt.%. R125 has almost identical charac-
teristics to R32, especially the same pressure levels (Figure 2.1.8) but with a much
higher specific heat capacity and it is not flammable. As a pure fluid, R125 performs
quite poorly as refrigerant and the coefficient of performance (COP) is quite low.
This is a consequence of the very low critical point of R125, while that of R32 is
rather high as compared to other refrigerants (Figure 2.1.8). The specific heat
capacity of R125 is rather high and thus it contributes to a reduced compressor
discharge gas temperature as compared to R32. Thus, R410A is nonflammable, has
an acceptable compressor discharge temperature, a high volumetric capacity, good
efficiency and a critical point that is lower than desirable. Under extreme air-
conditioning situations, the critical point can be reached or exceeded.
R407C consists of R32/R125/R134a, 23/25/52 wt.%. With the addition of R134a,
the vapor pressure is reduced and essentially matches that of R22. The mixture is not
flammable, the compressor discharge temperature is considerably lower than that of
R32 and the performance is acceptable. The critical point is higher than that of
R410A and it is not prone to be reached under extreme air-conditioning applications.
R507A consists of R125/R143a, 50/50 wt.%. This mixture is designed as a long-
term substitute for R502, a CFC-containing azeotrope. R404A consists of
R125/R143a/R134a, 44/52/4 wt.%. With the addition of R134a, the suction vapor
density matches that of R502. This mixture is designed to retrofit R502.
REFERENCES
Alefeld, G. and R. Radermacher, 1994, Heat Conversion Systems, CRC Press, Boca Raton, FL.
Allied Signal Chemicals, 1999, Genetron Products Brochure.
American Society of Heating, Refrigerating, and Air-Conditioning Engineers, Inc., 1997,
ASHRAE Handbook — Fundamentals, pp. 19.8–19.60.
Atofina Chemical, 1999, Website: http://www.atofinachemicals.com/newelf/fluorochem/pdf/
6049.pdf
Bosnjakovic, F., 1965, Technical Thermodynamics, Holt, Rinehart & Winston, New York, NY.
Calm, J.M., 1995, Refrigerant Database, ARTI Report, DOE/CE23810-59C.
Downing, R.C., 1988, Fluorocarbon Refrigerants Handbook, Prentice Hall, Englewood Cliffs,
NJ.
DuPont Fluorochemicals, 2000, “Technical Information for Suva Refrigerants,” Website:
http://www.dupont.com/suva/na/usa/literature.
Fairchild, P.D., 2000, Personal communication.
Granyrd, E., J.C. Conklin and J.R. Sand, 1991, “Advantage of Enthalpy-Temperature Dia-
grams for Nonazeotropic Refrigerant Mixtures,” Proceedings of XVIIIth Congress
of Refrigeration, Montreal, Quebec, Canada.
Godwin, D.S., 1994, “Results of Soft-Optimized System Tests in ARI’s R-22 Alternative
Refrigerants Evaluation Program,” Proceedings of The 1994 International Refriger-
ation Conference, West Lafayette, IN, pp. 7–12.
Herold, K.E., R. Radermacher and S.A. Klein, 1996, Absorption Chillers and Heat Pumps,
CRC Press, Boca Raton, FL.
Hughes, M., 1997, “Contemporary Fluorocarbons, Refrigerant for the 21 Century,” Proceed-
ings of ASHRAE/NIST Refrigerants Conference, pp. 117–121.
Hwang, Y., J.F. Judge and R. Radermacher, 1995, “An Experimental Evaluation on Medium
and High Pressure HFC Replacements for R-22,” Proceedings of The 1995 Interna-
tional CFC and Halon Alternatives Conference, Washington D.C., pp. 41–48.
McLinden, M.O., S.A. Klein, E.W. Lemmon and A.P. Peskin, 1998, “REFPROP, NIST
Thermodynamic Properties of Refrigerants and Refrigerant Mixtures Database,”
Version 6.0, Thermophysics Division of National Institutes of Standards and Tech-
nology, Gaithersburg, MD.
Perry, H.R., D.W. Green and J.O. Maloney, 1997, Perry’s Chemical Engineers’ Handbook
(7th edition), McGraw-Hill, New York, NY, pp. 4–12.
Radermacher, R. and D.S. Jung, 1992, “Theoretical Analysis of Replacement Refrigerants
for R-22 for Residential Uses,” U.S. Environmental Protection Agency Report, U.S.
EPA/400/1-91/041.
Richard, R. and L. Shankland, 1992, “Flammability of Alternative Refrigerants,” ASHRAE
Journal, Vol. 24, No. 4, pp. 20–24.
Sami, S.M., 1994, “A New Alternative HFC Blend for HCFC-22 and CFC-502,” Proceedings
of the 1994 International CFC and Halon Alternatives Conference, Washington D.C.,
pp. 56–64.
Siva, G. and D.R. Gustavo, 1999, “Total Equivalent Warming Impact of R22 Alternatives in
Air-Conditioning and Heat Pump Application,” ASHRAE Transactions, Vol. 105, Pt.
1, pp. 1228–1236.
Underwriters Laboratories Inc., 1994, UL Standard 2182, Refrigerants.
Vineyard, E.A., J.R. Sand and T.G. Statt, 1989, “Selection of Ozone-Safe, Nonazeotropic
Refrigerant Mixture for Capacity Modulation in Residential Heat Pumps,” ASHRAE
Transactions, Vol. 95, Pt. 1, pp. 34–46.
3 Vapor Compression
Cycle Fundamentals
The vapor compression cycle is the underlying thermodynamic process for most
refrigeration systems in stationary and many mobile applications. This cycle is also
referred to as the reverse Rankine cycle or the Perkins/Elmer cycle. For this text,
the term vapor compression cycle is used throughout. As a general introduction and
to establish the connection to the material taught in basic thermodynamics, the
Carnot cycle will be explained first and then the vapor compression cycle will be
discussed in full detail. This chapter also provides a description of the operation of
heat pumps within the larger context of energy conversion systems.
3.1 THE CARNOT CYCLE

The Carnot cycle is an example of an idealized energy conversion cycle. Figure 3.1.1
shows a Carnot cycle for power generation on a temperature-entropy (T-s) diagram.
Conventionally, in this chapter all temperatures are absolute values. The process line
AB represents the isothermal addition of heat Q2 at the temperature T2 to a working
fluid. We use here the convention that an arrow pointing to a process line represents
energy supplied to the cycle. Line BC represents the isentropic production of work,
CD the isothermal rejection of heat Q1 at the temperature T1 and DA the isentropic
input of work. When all processes are reversible, the area enclosed by ABCD
represents the net amount of work produced, W, and the area CDEF the amount of
thermal energy Q1 rejected by the cycle assuming E and F are located at T = 0 K.
For a work-producing process, as shown in Figure 3.1.1, the processes follow a
clockwise direction in the T-s diagram. The sum of the two areas CDEF and ABCD
is the amount of heat Q2 (thus area ABFE) supplied to the cycle as required by the
First Law of Thermodynamics,
Q2 = Q1 + (Winput − Woutput ) (3.1)
The signs of the quantities in Equation 3.1 are to be selected as indicated in Figure
3.1.1. All energies are counted as positive in the direction of the arrows. The
efficiency for power generation is defined as the amount of work produced divided
by the amount of heat supplied at the high temperature,
W
η= (3.2)
Q2
65
Q2
T
A B
T2
Winput Woutput
T1
D C
Q
1
E F
0 s
FIGURE 3.1.1 The Carnot cycle for power generation on a temperature-entropy diagram.
For the Carnot cycle of Figure 3.1.1, the Second Law of Thermodynamics states
that for reversible operation the net entropy production is zero, so that
Q2 Q1
− =0 (3.3)
T 2 T1
Equation 3.2 can be modified to an expression that contains only temperatures using
Equations 3.1 and 3.3 by eliminating W,
T2 − T1
η= (3.4)
T2
The expression in Equation 3.4 is frequently termed the Carnot efficiency factor for
power generation.
Figure 3.1.2 shows a Carnot cycle that is operated as a heat pump cycle. The
direction of all processes is reversed compared to the power generation cycle. Here,
the temperatures are chosen such that heat Q0 is added to the working fluid at T0
along the process line GH, the fluid is compressed isentropically, HI, heat Q1 is
rejected at T1, IJ, and the fluid is expanded isentropically, JG. Again, the areas
represent energy transfers for reversible processes. The net amount of work input
required for this cycle is represented by the area GHIJ and the amount of heat
absorbed by the area GHKL. The sum of both areas (area IJLK) represents the
amount of heat rejected at T1.
The performance of a heat pump is described by the ratio of the benefit obtained —
the amount of heat available at the high temperature — divided by the expenditure,
the net work requirement. Since this value is always greater than 1.0, the term
coefficient of performance (COP) is customary,
Vapor Compression Cycle Fundamentals 67
Q1
J I
T1
Woutput Winput
T0
G H
Q0
L K
0 s
FIGURE 3.1.2 The Carnot cycle for heat pumping on a temperature-entropy diagram.
T1
COP = (3.5)
T1 − T0
This equation is derived by using the First and Second Laws for the heat pump
process of Figure 3.1.2 and by following the same procedure as for Equation 3.4.
The Carnot cycle of Figure 3.1.2 can also be used for cooling or refrigeration
applications. While the cycle itself does not change, the way we view the application
is different. For refrigeration, the heat removed at T0 is of interest and the COP is
defined as the ratio of the cooling capacity Q0 over the work input. Subscript R is
used to designate that the COP is defined for refrigeration,
T0
COPR = (3.6)
T1 − T0
Equation 3.6 is derived by applying the First and Second Laws as described above
for the power generation cycle. For the coefficients of performance of a heat pump
cycle and refrigeration cycle, the following relationship can be derived. This expres-
sion can be verified by substituting Equations 3.5 and 3.6 into Equation 3.7,
COPR + 1 = COPH (3.7)
3.2 HEAT PUMPS IN THE CONTEXT

OF ENERGY CONVERSION
To discuss the function of a heat pump within the larger context of energy conversion,
a set of Carnot cycles is used. Now both cycles (the work producing and refrigeration
Q2
T
A B
T2
W
Q”1
J I
T1
D C
Q’1
T0
G H
F Q0
E L K
0 s
FIGURE 3.2.1 Carnot cycles for a combined power-generation/heat pumping facility such
as an engine driven or absorption heat pump.
cycle of Figures 3.1.1 and 3.1.2) are considered together. It is assumed that the
amount of work produced by the first cycle, Figure 3.1.1, is identical to the amount
of work required by the second cycle, Figure 3.1.2. The new device, Figure 3.2.1,
raises the temperature level of heat supplied at T0 to T1 by using the thermodynamic
availability of the high temperature energy supplied at T2. The waste heat of the
power generation portion of this combined cycle is also rejected at T1. Thus the total
amount of heat rejected at T1 has two contributions, Q′1 and Q″1 .
This combined cycle represents a heat pumping device that is driven by the input
of heat only. This model is a reflection of the fact that most of the power available
today is generated in a heat engine. Although this text focuses on the vapor com-
pression cycle that is driven by the input of power, in a larger context primary energy
made available mostly in the form of heat is the source of the power supplied to
heat pumps. Thus, Figure 3.2.1 is the ideal representation of several different heat
pumping concepts. Examples are an engine-driven vapor compression heat pump,
a combination of a steam or gas turbine power plant with an electrical vapor
compression heat pump or the representation of absorption or adsorption heat pump.
The coefficient of performance for the combined device is customarily defined as
Q0
COPAR = (3.8)
Q2
for cooling and refrigeration applications and as
Q1′ + Q1′′
COPAHP = (3.9)
Q2
for heating applications.

By applying the First and Second Laws and eliminating either Q0 or Q1 (with
Q1 = Q′1 + Q″1 ), Equations 3.8 and 3.9 can be converted into expressions that depend
on temperature only:
T2 − T0 T1
COPAHP = (3.10)
T2 T1 − T0
T2 − T1 T0
COPAR = (3.11)
T2 T1 − T0
Here, the distinction between a heat pump and a refrigeration system is only a
function of the application, not of the operating mode. Equation 3.7 is also valid for
any heat driven heat pump:
COPR + 1 = COPHP (3.12)
In Figure 3.2.1, it is implied that the power-producing cycle is operating at higher

temperature levels than the heat pump cycle. This does not have to be the case. It
is conceivable that applications call for the power being generated at temperature
levels below those of the heat pump application. For example, a portion of waste
heat from an industrial plant can be used to operate a power producing Rankine
cycle and this power then drives a heat pump that lifts the remaining portion of the
waste heat to a higher temperature level. Absorption heat transformers are an example
of such systems.
3.3 THE IDEAL VAPOR COMPRESSION CYCLE

Figure 3.3.1 shows schematically the ideal vapor compression cycle. Figure 3.3.1(a)
shows the cycle schematic and in Figure 3.3.1(b) the same state points are super-
imposed on a ln(P)-h diagram. Isentropic compression occurs from point 1 to 2 and
isobaric heat rejection from point 2 to 3, representing the desuperheating of the
vapor. The process from point 3 to 4 is the isobaric and isothermal heat rejection
due to condensation and point 4 to 5a the isentropic expansion. The state points for
the ideal vapor compression cycle can be located on the ln(P)-h diagram with only
minimal information about the operating conditions and the assumption of an ideal
cycle.
The ideal vapor compression cycle used in this text is defined as follows: no
pressure drop in any heat exchanger and connecting piping, saturated vapor is leaving
the evaporator, saturated liquid is leaving the condenser, the expansion process is
the isenthalpic process line 4–5 and the compression process is isentropic. When
these conditions are fulfilled, one has to specify only two items of information to
3
4 Condenser 2
Expansion
Compressor (a)
Va lve
Evaporator
5 1
ln (P)
4 3 2
(b)
5a 5 1
FIGURE 3.3.1 (a) Schematic of a vapor compression cycle. (b) Schematic of ln(P)-h diagram
with the state points of a vapor compression cycle superimposed.
plot the cycle on the ln(P)-h diagram, the saturation pressure or temperature for the
evaporator and the saturation temperature or pressure for the condenser.
To demonstrate this concept, the refrigerant ammonia is selected as an example.
The saturation temperature of the evaporator is assumed to be –20˚C and that of the
condenser 40˚C. The ln(P)-h diagram is shown in Figure 3.3.2. With the knowledge
of the evaporator saturation temperature, state point 1 is defined, located on the
saturated vapor line at the intersection with the isotherm of –20˚C. The saturation
pressure can be read from the pressure axis as about 0.19 MPa. Points 3 and 4 are
found from the knowledge of the condenser saturation temperature and the intersec-
tion with the saturated vapor and saturated liquid lines, respectively. The condenser
saturation pressure is read to be 1.7 MPa. Point 2 is found by following a line of
constant entropy from point 1 to the intersection with the isobar of the condenser
saturation pressure. Since the expansion process is isenthalpic, point 5 is found
vertically below 4, that is, the intersection of the line of constant enthalpy and the
evaporator isobar. With this, the ideal vapor compression cycle is completely defined
on the ln(P)-h diagram. In most cases, it is best to start plotting the ideal vapor
compression cycle on the ln(P)-h diagram by finding points 1 and 4; then all others
are fixed.
There seem to be two dominating reasons why the vapor compression cycle is
the cycle of choice for a wide range of refrigeration applications. One reason is the
fact that the latent heat during the liquid-vapor phase change process is used as the
mechanism to transfer heat to and from the working fluid. This greatly reduces the
mass flow rate in the cycle. But at least as important is the following consideration:
All other refrigeration cycles involve the exchange of work twice, once in a com-
pression process and once in an expansion process. The difference between these
two contributions of work is the net work input for a heat pump. When each of the
two processes that involve work has a realistic efficiency (for example, 0.8), the net
work is to be divided by an overall efficiency of 0.64. This efficiency of the cycle
4 3 2
5 1
FIGURE 3.3.2 ln(P)-h diagram of ammonia vapor compression cycle. (Copyright 2001, American Society of Heating, Refrigerating, and

is applied in addition to the thermal efficiency and represents significant performance

degradation. The vapor compression cycle avoids this shortcoming with an elegant
approach. One of the two isentropic processes that involve work, the expansion
process, is conducted almost entirely in the liquid phase. Since liquids are essentially
incompressible, only a minute amount of work is lost as compared to the expansion
of a gas.
3.3.1 POWER AND CAPACITY CALCULATIONS

The ln(P)-h diagram of Figure 3.3.2 is a very informative design tool that merits an
understanding of more of its general features in order to quickly gain numerical
information about the cycle. First, the amounts of heat and work that are involved
are calculated.
Any steady-state thermodynamic analysis starts out with two basic laws of
conservation. The first is the conservation of mass, the second the conservation of
energy. The compressor is considered first: A mass balance for the compressor is
based on the observation that for a steady state, steady flow process — assumed to
be the case here — the mass flow that enters must also be leaving. Thus the mass
balance states
m 1 = m 2 = m (3.13)
The energy balance states that all energy supplied to the compressor has to leave it
also under steady state condition without considering compressor losses. The mass
flow rate entering equals the mass flow rate leaving. In fact, since the ideal vapor
compression cycle is a closed system as can be seen from Figure 3.3.1(a), this
equation holds for all components of the cycle (W is replaced by Qi as appropriate),
m 1h1 + W = m 2h2 (3.14)
Rearranging Equation 3.14 and using 3.13, the power input, W, can be calculated as
W = m (h2 − h1) (3.15)
In a similar fashion, the amounts of heat exchanged in the evaporator, Qevap, and
condenser, Qcond, can be calculated as follows:
Q evap = m (h1 − h5 ) (3.16)
and
Q cond = m (h2 − h4 ) (3.17)

The energy balance must also be fulfilled for the overall cycle. It is left to the reader
to show that
Q evap + W − Q cond = 0 (3.18)
Equation 3.18 serves as a good check to confirm that the above calculations are
internally consistent.
Figure 3.3.2 reveals additional useful information. The temperature of the vapor
leaving the compressor can be read from the chart, in this case about 141˚C. Further,
point 5 is located in the two-phase range. Using the lines of constant vapor quality,
x, the quality at the evaporator inlet, is determined to be 0.22. This indicates that
22% of the stream entering the evaporator is already evaporated. This evaporation
has to occur to ensure that the entire stream is cooled to the evaporator saturation
temperature.
3.4 DIFFERENCES BETWEEN THE CARNOT CYCLE

AND VAPOR COMPRESSION CYCLE
Figure 3.4.1 shows side-by-side the Carnot cycle (a) and the vapor compression
cycle (b), each superimposed on a temperature-entropy diagram. Both are repre-
sented as ideal cycles for which realistic effects such as pressure drop or compressor
inefficiencies are not accounted. The arrows indicate the direction in which the cycle
progresses. There are two obvious ways that the vapor compression cycle deviates
from the Carnot cycle. These are the so-called superheat horn and the expansion
process. Both are shown in more detail in Figure 3.4.2. The superheat horn results
from the fact that for most common refrigerants, the fluid leaving the compressor
is superheated.
The superheat horn presents a performance penalty. It represents increased
compressor work as compared to the Carnot cycle. This is indicated by the increased
area enclosed by the cycle, which in a T-s diagram represents work. In this case of
T T
s s
(a) Carnot Cycle (b) Vapor Compression Cycle
FIGURE 3.4.1 Schematic of Carnot cycle (a) and vapor compression cycle (b) in a T-s
diagram.
T
Isenthalpic
Expansion
Superheat
Horn
Isentropic
Expansion
FIGURE 3.4.2 Isenthalpic and isentropic expansion for a vapor compression cycle in a T-s
diagram.
a counterclockwise cycle, it represents compressor work input. The Carnot cycle is

fluid independent and the superheat horn can be avoided. For the vapor compression
cycle, it could also theoretically be avoided. For example, the evaporation process
could be terminated at a quality selected such that the compressor outlet would be
just saturated vapor. The compressor work input would be lower; however, the
compressor suction would contain a considerable amount of liquid, a condition that
would damage many compressors. The reason for the reduced compressor work is
that in the case of the lower discharge temperature, less of the compressor work
goes into heating the fluid and the compressor does not have to work as much against
an increasingly hotter gas, as is the case when vapor alone is compressed. This
observation also indicates that the specific heat capacity of the refrigerant vapor is
an important variable influencing compression efficiency.
The expansion process for the vapor compression cycle is an isenthalpic process,
while it is isentropic for the Carnot cycle. This simultaneously contributes two
penalties, loss of work and loss of capacity. This is shown once more in Figure 3.4.3
Isenthalpic
ln(P) Expansion
Isentropic 4 3 2
Expansion
5a 5 1
FIGURE 3.4.3 Isenthalpic and isentropic expansion for a vapor compression cycle in an
ln(P)-h diagram.
in a ln(P)-h diagram. The enthalpy difference h5 – h5a represents the loss of work.
This energy, when not extracted from the fluid, results in an increased vapor quality.
Consequently, less liquid refrigerant is present to provide cooling.
It was shown in a previous chapter that the amount of work lost in the expansion
process is small and usually readily accepted. The superheat horn is not easily
avoided with the constraints imposed by conventional technology. Figure 3.4.4 puts
these contributions more clearly in perspective (Domanski, 1995). It shows the
relative penalties of the superheat horn and the expansion process. The term relative
penalty is defined as follows: The relative penalty for the loss of cooling capacity
is expressed as Qexp /QC, which stands for “capacity with isenthalpic expansion”
divided by the “capacity with isentropic expansion;” further, Wexp /WC expresses the
ratio of the respective work terms related to the expansion process and Wsup /WC the
additional work because of the superheat horn. In Figure 3.4.4, these losses are
graphed on the same bar chart as stacked bars for a large number of refrigerants.
The x-axis of Figure 3.4.4 shows the refrigerants sorted according to their vapor
specific heat capacity. For ammonia, the refrigerant with the lowest heat capacity,
the two work effects have more or less the same relative penalty. With increasing
heat capacity, the effect of the superheat horn vanishes while both of the remaining
penalties increase and the expansion process quickly becomes the most dominant
one. It should be noted that the relative penalties are not indicative of how much
each loss contributes to an overall degradation to COP. A more detailed analysis is
given in Domanski (1995). Figure 3.4.4 shows how the penalties vary with the
specific heat capacity of the refrigerant. This makes clear that the specific heat
capacity of a refrigerant has an important influence on system performance, resulting
in two effects. To better understand this, it is assumed for the following that a given
refrigerant has a high specific heat capacity. It is assumed also, without limiting the
general validity of the following consideration, that a positive displacement com-
pressor is used.
The temperature increase during the compression process is low. This results
from the fact that the compressor work is turned into the internal energy of the gas
within the compressor. There are several options to increase the internal energy of
a gas. Energy can be stored within molecules in the form of rotational or oscillatory
motion or in the form of translational energy, i.e., the speed at which the molecule
moves, its kinetic energy. Only the latter results in a temperature increase.
When the specific heat capacity of a gas is high, a considerable amount of the
increase in internal energy is stored within the molecule and only a small fraction
leads to an increase in kinetic energy, that is, its temperature. The temperature
increase requires increased compression work. For fluids of high specific heat capac-
ity, this effect is smaller than for fluids with low specific heat capacity. Thus, when
the compressor compresses a gas that stays relatively cool, the compressor work is
not as high as if the specific heat capacity were low and the temperature of the gas
increased more quickly.
On the other hand, during the expansion process of a fluid with a large specific
heat capacity, a relatively large amount of refrigerant has to evaporate to cool the
remaining liquid to the evaporator saturation temperature and less liquid is left to
provide cooling capacity.

Relative Penalty
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
R-744
NH3
R-32
R-14
Qexp/QC
R-23
Wsup/WC
Wexp/WC
R-C270
R-22
R-13
R-13B1

R-152a
R-21
R-290
R-143a
R-12
R-143
R-134a
R-142b
R-125
R-11
R-134
R-600a
R-124
R-141b
E134
R-115
R-600
R-123
R-123a
R-245cb
FIGURE 3.4.4 Relative penalties of the superheat horn and expansion process (Domanski, 1995).
R-114
R-236ea
R-227ea
I-C5
R-113
N-C5
R-218
E-245
R-C318
ln (P) ln (P)
h h
(a) (b)
FIGURE 3.4.5 Schematic of vapor compression cycle in a ln(P)-h diagram for a fluid of low
(a) and high (b) specific heat capacity.
This situation is better understood when the ln(P)-h diagram for a refrigerant of
high specific heat capacity is compared to one with low specific heat. Figure 3.4.5
shows the two diagrams side by side. Figure 3.4.5(a) shows the diagram of a low
heat capacity refrigerant; Figure 3.4.5(b), that of a high heat capacity fluid. Obvi-
ously, the vapor dome is tilted much more to higher enthalpies for the high capacity
fluid. As a consequence, the expansion process produces much more vapor and less
liquid and the evaporator capacity is reduced considerably. Furthermore, the com-
pression stays very close to the saturated vapor line and the compressed vapor is
almost not superheated at all. In fact, for some refrigerants, the state point of the
compressed vapor might be located in the two-phase range. In practice, avoiding a
two-phase stream leaving the compressor involves sufficiently superheating the
suction vapor. The penalty in terms of increased compressor work is small or even
desirable to avoid a two-phase condition at the compressor outlet.
3.5 REALISTIC VAPOR COMPRESSION CYCLES

In Section 3.3, the ideal vapor compression cycle was introduced. However, under
realistic operating conditions, several effects must be considered that significantly
impact the cycle performance.
A process scheme of a realistic vapor compression system is shown in a ln(P)-h
diagram in Figure 3.5.1. This figure also shows a schematic of the vapor compression
cycle. The state points in the schematic correspond to those in the ln(P)-h diagram.
In comparison to the ln(P)-h diagram of Figure 3.3.1, the first major deviation that
is immediately obvious is the slope in the process lines that used to be isobars. Since
the refrigerant has to flow through the heat exchangers and any connecting piping,
a certain pressure drop is necessary. This is reflected in the diagram of Figure 3.5.1
by the slope in the process line for the evaporation process, line 5–1, for the
desuperheating process, line 2–3, and the condensation process, line 3–4a.
Starting with the evaporator outlet and following the refrigerant around the cycle,
note that the refrigerant is superheated, line 1–1a. The superheating is desirable for
two reasons: First, it ensures that all the refrigerant is evaporated where it can

4a 3
4 Condenser 2
(a)
Expansion
Compressor
Va lve
Evaporator
5 1a
1
ln (P)
2s 2
3
4a
4
(b)
5 1 1a
FIGURE 3.5.1 (a) Schematic of vapor compression cycle with state points to explain realistic
operating conditions. (b) Schematic of realistic vapor compression cycle on a ln(P)-h diagram.
Superheat (1–1a), subcooling (4a–4) and pressure drop (slant in line 2–4 and 5–1a) are
included.
contribute to the cooling capacity. Second, superheating usually occurs within the
evaporator for the purpose of ensuring that the compressor receives only vapor
without any liquid entrained that could damage the compressor.
Due to the pressure drop in the evaporator and the superheating at the evaporator
outlet, the compression process starts at a lower pressure and further into the
superheated vapor region than in Figure 3.3.1. This is a double penalty for the
compressor. A higher-pressure difference needs to be overcome by the compressor
and the work also increases due to the higher temperature of the suction vapor. An
inspection of the ln(P)-h diagrams, Figures 2.1.12 through 2.1.24, reveals that the
slope of the isentropes decreases as the enthalpy increases, i.e., as the state point
moves further away from the two-phase region. Thus, for isentropic compression,
the compressor work increases once again as the entering suctioned gas is super-
heated more.
Furthermore, the compressor must overcome the pressure drop of the refrigerant
in the discharge line and the condenser, yet another increase in compressor work
compared to the ideal cycle. The entire compression process is represented by the
process line 1a–2. Since the compression process is usually irreversible to some
degree due to internal friction of the mechanical parts, heat transfer and valve
pressure drop, point 2 lies to the right of the endpoint 2s that would be achieved
with isentropic compression. An additional penalty is increased volume, reducing
capacity for a given displacement.
The process line 2–3 represents the desuperheating process in the condenser and
line 3–4a the condensation process. Both exhibit the necessary pressure drop. Line
4a–4 represents the subcooled region, where the condensate is cooled to a lower
temperature.

In many applications, it is important that the refrigerant leaving the condenser

is subcooled. This ensures that only liquid and no vapor bubbles enter the expansion
device, allowing for better flow control and smaller devices. Also, if vapor bubbles
were to enter the expansion device, there would be less liquid refrigerant available
in the evaporator to produce cooling while the compressor still has to compress that
portion of the vapor that did not contribute to the cooling capacity. This represents
a loss of capacity and efficiency. Alternatively, too much subcooling indicates that
a considerable portion of the condenser volume is filled by single-phase liquid. Thus,
the area available for heat rejection from the condensing fluid is smaller than it could
be. As a consequence, the saturation temperature is increased along with the satu-
ration pressure. The compressor work increases as a result.
It can be stated that the degree of subcooling at the condenser outlet is primarily
determined by the amount of refrigerant charged to a heat pump and the setting of
the expansion device primarily determines the degree of superheat at the evaporator
outlet.
3.6 LORENZ CYCLE

The Carnot cycle is based on the assumption that the cycle accepts and rejects heat
at a constant temperature level. However, in many applications, heat is supplied by
or rejected to a fluid which changes its temperature. Examples are the chilled water
produced by a chiller or the air or cooling water to which an air conditioner rejects
heat. Figure 3.6.1 presents the schematic of such heat exchange processes for a given
refrigerant using a T-s diagram. Process line 1–2 represents the evaporating refrig-
erant and process line 3–4 the chilled water being cooled. The latter is superimposed
on the T-s diagram of the refrigerant merely for indicating the water temperatures
in comparison to those of the refrigerant. Line 5–6 represents the condensing refrig-
erant and line 7–8 the cooling water as it is being heated. At points 1 and 4 and at
points 5 and 8, a so-called pinch point can be observed where the temperature
Condensing
T 5 Refrigerant 6
8
7 Cooling Water
3
4 Chilled Water
1 2
Evaporating
Refrigerant
s
FIGURE 3.6.1 The evaporating temperature (1,2) and condensing temperature (5,6) are fixed
by the lowest chilled water (4) and highest cooling water (8) temperature, respectively. A
pinch point occurs at (1,4) and (5,8).

differences between both fluid streams become very small. As a consequence, the
heat transfer rate becomes small as well. A pinch point limits the heat transfer rate
due to very small approach temperatures. In order for a heat exchanger to still
facilitate heat exchange, the available heat transfer surface area must increase.
However, in this case the entropy production is also small due to the fact that heat
is transferred over a small temperature difference. In contrast, at points 2 and 3 and
also for 6 and 7, the temperature differences are large, the heat transfer rate is large
as well and so is the entropy production.
Note that even when the heat transfer area approaches infinity, the performance
improvement of the heat exchanger is limited (Rice, 1993a). While the temperature
difference at the pinch point approaches zero, the temperature differences at the
other end of the heat exchangers stay finite and the entropy production approaches
a finite value. In case of the evaporation and condensing processes in Figure 3.6.1,
the highest temperature of the evaporating refrigerant and the lowest temperature of
the condensing refrigerant are fixed by the respective water temperatures. In turn,
their pressures are fixed and thus the compressor power, so even with heat exchanger
areas approaching infinity, the entropy production in the heat exchangers cannot be
reduced to zero and the performance improvement of the entire heat pump is severely
limited.
The Lorenz cycle addresses this issue (Herold, 1989; Alefeld, 1987). When a
working fluid is available that changes its temperature during the course of the evapo-
ration or condensing process (i.e., it has a temperature glide as described in Chapter 2),
then the schematic of Figure 3.6.1 can be modified as shown in Figure 3.6.2.
In the ideal case that the change in temperature from the beginning to the end
of the evaporation process matches that of the chilled water, both process curves
become parallel and the pinch point is eliminated. Figure 3.6.2 shows the Lorenz
cycle. With an increase in heat transfer area, the temperature difference between the
two fluids continues to shrink everywhere in the exchanger and thus the overall
entropy production can theoretically approach zero. Assuming that the cooling and
chilled water temperatures are given, the suction and discharge pressures can
T Condensing Refrigerant
6
8
5
7 Cooling Water
4 Chilled Water 2
1 Evaporating Refrigerant
FIGURE 3.6.2 When the refrigerant saturation temperature has a glide, the pinch point can
be eliminated.

approach each other to the largest possible extent, certainly much further than in
the case shown in Figure 3.6.1. The overall efficiency of the cycle improves to the
largest possible extent, too. It should be noted that even for the same heat exchange
area, a Lorenz cycle that better matches the source and sink glides gives a higher
cycle efficiency because it operates at an improved mean temperature than the
corresponding pure refrigerant (Rice, 1993b).
The mixtures of Chapter 2 have the potential to approach the requirements of
the Lorenz cycle depending on the degree to which they match the application glide
in both the evaporator and the condenser. It is interesting to observe that for the
given chilled and cooling water temperatures of Figure 3.6.2, the Carnot cycle, also
symbolized by the process lines in Figure 3.6.1 (1–2–6–5), should have lower
efficiency than the Lorenz cycle of Figure 3.6.2 (1–2–6–5). After all, in a T-s diagram,
the area enclosed by the process represents the required work input as long as all
processes are reversible. This condition is fulfilled here. The reader might have the
expectation that no thermodynamic cycle can exceed the performance of the Carnot
cycle.
Both statements are correct. Upon closer examination, the Lorenz cycle does
not exceed the performance of Carnot cycles. This can be demonstrated with the
help of Figure 3.6.3. The Lorenz cycle as shown in Figure 3.6.3 can be approximated
by a series of Carnot cycles that are superimposed on the Lorenz cycle in a step-
like fashion. In the limiting sense that the Carnot cycles have an infinitesimal length
in the s-direction, they approach the Lorenz cycle.
Thus, the performance of the Lorenz cycle can be approximated through a series
of Carnot cycles and therefore the Second Law is not violated. In general, the
performance of many systems can be improved when a series of Carnot cycles (or
more realistic cycles) are used that more closely match the temperature profiles of
heat sinks and heat sources.
1
s
FIGURE 3.6.3 The Lorenz cycle (1–2–6–5) can be approached by many Carnot cycles
(small, vertical rectangles), when operated such that they approximate the Lorenz cycle.

3.7 VAPOR COMPRESSION CYCLE WITH ZEOTROPIC

MIXTURES IN THERMODYNAMIC DIAGRAMS
This chapter discusses the vapor compression cycle for zeotropic mixtures in light
of the thermodynamic diagrams introduced in Chapter 2. This facilitates an under-
standing of the effects that mixtures have on the cycle performance. We focus on
the ideal vapor compression cycle and binary mixtures for the sake of simplicity.
3.7.1 PRESSURE-TEMPERATURE DIAGRAM

Figure 3.7.1 shows the pressure-temperature diagram in two versions, for pure
components (a) and for zeotropic mixtures (b). The mixture has the two constituents,
A and B, and the vapor compression cycle is superimposed on each. The numbers
for the state points are the same for both diagrams and for the inset of the vapor
compression cycle schematic. For the pure fluid, all two-phase state points collapse
onto the saturation line that separates the vapor and liquid regions. The state point
2 of the end of the compression process is located in the superheated vapor region.
However, it becomes apparent that this diagram is very suitable for looking at overall
operating conditions such as the relationships between pressure and temperature
levels. It does not provide much detail about the processes within the heat exchangers.
For the mixture, we see more detail within the heat exchangers. Because of the
glide, the inlet and outlet conditions are clearly distinguished and one can even see
that the inlet quality to the evaporator has a value between 0.0 and 1.0. The meaning
and location of state point 2, the compressor outlet, can be confusing and needs
further explanation. Point 2 is plotted so that pressure and temperature of that state
are correctly represented but it may be located within the solution field created by
3
4 Condenser 2
5 Evaporator 1
ln (P) Critical Point ln (P)

Liquid
A
B
re
re
Vapor
Pu
Pu
3,4 4
Condenser 2
2 3
Evaporator
5,1 5 1
−1/T −1/T
(a) (b)
FIGURE 3.7.1 Vapor compression cycle superimposed on a ln(P)-(–1/T) diagram.

Vapor Pressure Lines for

ln (P) Several Refrigerants
High Side
Pressure Limit
Low Side
Pressure Limit
Evaporation Condensation −1/T

Refrigerant Lies
Within Window Temperature Temperature
FIGURE 3.7.2 When a vapor pressure curve of a given refrigerant is located within the
window, then it is suitable for the intended application. The window is specified through the
desired evaporator and condenser temperatures and the acceptable high and low pressure
limits.
the vapor pressure lines of the pure fluids A and B. This could imply that the outlet
condition is a two-phase fluid. It must be understood that each of the vapor pressure
lines is an isostere, a line of constant mass fraction. Each of the lines separates a
liquid and a vapor region for a mixture of that particular mass fraction. Thus, when
point 1 indicates saturated vapor leaving the evaporator, any point to the right of
that particular isostere represents superheated vapor with regard to that isostere.
In most pressure-temperature diagrams, there are no provisions to indicate the
dew points. The vapor curves shown indicate only bubble points. The user must find
the information about dew points 1 and 3 from another diagram or source. Thus,
the observer must understand the cycle and the diagram quite well to correctly
comprehend the meaning of point 2.
The pressure-temperature diagram is nevertheless a good tool to gain insight
about pressure and temperature relationships. For example, it allows a quick screen-
ing to determine which fluid is suitable for a given application. An application is
determined by the expected temperature levels of the evaporator and condenser and
by pressure limitations. The latter are dictated by two considerations: The first
limitation is the maximum pressure rating for commercially available components
and the second is given by what suction pressure is deemed acceptable for the
compressor. These values create a window as shown in Figure 3.7.2.
3.7.2 PRESSURE-ENTHALPY DIAGRAM

Figure 3.7.3 shows the ln(P)-h diagram for a zeotropic mixture with superimposed
state points of the vapor compression cycle. The topography of the cycle and its

T3
T4 T4a
ln (P)
3 2
4 4a
T5a
5
1 1a X = Const
T1
T5
h
FIGURE 3.7.3 ln(P)-h diagram for a zeotropic mixture, with the state points of the vapor
compression cycle superimposed.
state points are the same as those for pure fluids. The difference lies in the underlying
fluid properties. Figure 3.7.3 shows, in addition to the cycle, the isotherms for the
state points in the two-phase region. In this way the temperature glide is represented
correctly. For example, in the evaporator the glide is T1–T5 and in the condenser
T3–T4a.
Upon closer inspection, Figure 3.7.3 reveals other important differences between
pure and mixed refrigerants in the vapor compression cycle. The temperature T5 is
higher than the liquid saturation temperature at the same pressure T5a. This indicates
that for mixtures, in contrast to pure fluids, the expansion process has two penalties.
There is less liquid to evaporate, which is the case for pure and mixed fluids, but
for mixtures, the temperature at the evaporator refrigerant inlet is not as low as it
could be without the flashing. This first loss, caused by the increased vapor quality,
affects the capacity and efficiency of the system and shows in the energy balance
for the evaporator. It is therefore termed a “First Law loss.” The second loss, the
temperature increase, does not show up in the energy balance but its effects are
clearly seen in a Second Law analysis. This situation is similar to the effects of the
glide. The fact that refrigerant mixtures have a glide is not immediately visible in
the equations of a First Law analysis using energy balances and is only apparent in
a Second Law analysis of the evaporator or condenser.
Nevertheless, when there is a Second Law benefit such as less entropy produc-
tion, it must show up in a better COP as well. With the glide, this benefit manifests
itself by an increase in suction pressure or a decrease in the discharge pressure as
discussed in Section 3.6; thus, the compressor work is reduced. The benefit that can
be attained when the amount of vapor produced during flashing is reduced is dis-
cussed in more detail later.
The reader should keep in mind that if the overall mass fraction changes for any
reason, this diagram is no longer valid and a new ln(P)-h diagram has to be generated
for the new mixture mass fraction.

T 2
P5
P3 3 P1
4
P4
5
1
X = Const
FIGURE 3.7.4 T-s diagram for vapor compression cycle. Pressure drop in the evaporator and
condenser is indicated through the slanted process lines 5–1 and 3–4.
3.7.3 TEMPERATURE-ENTROPY DIAGRAM

Figure 3.7.4 shows the schematic of a T-s diagram for a mixture with the vapor
compression cycle superimposed. In the two-phase region of the T-s diagram, the
isobars have a positive slope. The line 5–1 shows clearly the pressure drop P5–P1
and how it offsets to some degree for the temperature glide, which would be more
pronounced if the pressure drop were zero. For the evaporator, this pressure drop
leads to a reduction in the temperature glide. While the temperature glide causes
the temperature of the two-phase refrigerant to increase from inlet to outlet, the
pressure drop causes this temperature to drop. These are two competing processes.
Thus the temperature glide in the evaporator is reduced for two reasons: the flashing
in the expansion valve and the pressure drop. These considerations influence the
mixture selection for a given application or in turn the selection of the most appro-
priate temperature glide of the heat transfer fluid.
In the condenser, the situation is reversed. The temperature glide of the mixture
and the glide caused by the pressure drop add up and the glide becomes larger. For
these reasons and the difference in pressure, the glides in the evaporator are always
smaller than those in the condenser. These effects are more obvious in this diagram
than in the ln(P)-h diagram described above.
In the T-s diagram, the influence of the compressor efficiency is more obvious.
This is another example of how important it is to choose the most appropriate
diagram to consider the question at hand. For a compressor of 100% efficiency, the
compression process is isentropic and the process line 1–2 is vertical. Similarly,
the expansion process is highly irreversible and the process line 4–5 reflects this as
well. The entropy increases during the expansion process.
As for a ln(P)-h diagram, the T-s diagram is only valid for a given mixture mass
fraction. If this mass fraction changes for whatever reason, a new T-s diagram must
be considered.

2
T
3
P = Pcond
X3’ 4 4a
X4’
1
5 P = Pevap
5a
X1’
X5’
X5’’
0.0 X1,2,3,4,4a,5,5a 1.0
X
FIGURE 3.7.5 T-x diagram with the state points of the vapor compression cycle superimposed.
3.7.4 TEMPERATURE-MASS FRACTION DIAGRAM

Figure 3.7.5 shows a schematic T-x diagram of a binary zeotropic mixture with the
vapor compression cycle superimposed. This diagram is rather unusual but it never-
theless reveals interesting features. The state points are again the same as in the
previous diagrams. The mass fraction that circulates within the heat pump is x1,
which is the same for all state points, i.e., x1 = x2 = x3 = x4 = x4a = x5 = x5a. Starting
with point 1, the saturated vapor leaving the evaporator, one follows the refrigerant
through the cycle. The compression process does not change the mass fraction but
the pressure and temperature are increased and superheated vapor at point 2 is
obtained. The vapor is cooled at constant mass fraction to saturated vapor, point 3,
and the first liquid droplet appears with the mass fraction of x3. At the end of the
condensation process, point 4 is reached with a mass fraction of the last bubble of
x4. If the liquid is subcooled, it reaches point 4a. The expansion process ends at
point 5, somewhere in the lower portion of the two-phase region at the evaporation
pressure level. The refrigerant is in equilibrium with a liquid phase of a mass fraction
x5 and a vapor phase of mass fraction x5. The evaporation process ends at point 1
with the last droplet having a mass fraction of x1.
The T-x diagram is not well-suited to locating certain state points that are
important for cycle design, such as points 2 and 5. But it demonstrates very well
how the mass fractions change in the heat exchangers. This information is very
important for detailed systems and heat exchanger design. The changes in mass
fraction influence transport properties and therefore heat transfer coefficients and
also the interaction with the compressor oil that is present in all parts of the system
at a highly variable mass fraction.
Probably the most important feature of the T-x diagram is its ability to make
intuitively clear that the mass fraction within the cycle can change for a number of
reasons. Since during the evaporation and condensation processes the mass fractions

of vapor and liquid are different, depending on its location, a system leak can cause
a shift in the mass fraction of the remaining refrigerant mixture. The same holds for
periods when the system is turned off. A heat pump is filled to about 30% of its
total volume with liquid refrigerant. The remainder is refrigerant vapor with a mass
fraction different from that of the liquid phase. Again, a leak that allows only vapor
or only liquid to escape causes the mass fraction of the remaining refrigerant to
shift. Since the liquid phase holds the bulk of the refrigerant mass, which is close
to the charged mass fraction, vapor leaks are more effective in changing the mass
fraction. The influence of leaks is discussed in more detail in Section 9.9.
3.8 THE MATCHING OF TEMPERATURE GLIDES

So far it is assumed that the temperature glides are linear. In Figure 3.6.1, straight
lines indicate glides but, in general, glides are not linear. It should be noted that
ternary mixtures tend to have a more linear glide than binary mixtures. Examples
of nonlinear glides are indicated in the ln(P)-h diagram schematic of Figure 2.1.27.
This nonlinearity introduces interesting challenges for the design of heat exchangers.
With a linear glide, the pinch point (the point of closest temperature approach
between the hot and the cold fluid) must be located at either end of the heat exchanger
or it does not exist when the two process lines are parallel. Possible cases are
indicated in Figure 3.8.1 with one cold fluid stream and three different hot fluid
streams. In general, there are three patterns of deviations, distinguished by their
geometric characteristics: concave, converse and s-shaped temperature glides. For a
given logarithmic mean temperature difference, the parallel case has the lowest
entropy production. The location of the pinch point can be controlled by selecting
the same thermal capacity (mass flow rate times specific heat capacity) for both
fluids.
Since the pinch point limits the heat transfer rate, its existence and location
severely affect heat exchanger performance. The following consideration is limited
to counterflow heat exchangers.
T
Hot Fluid 1
Hot Fluid 3
Hot Fluid 2
Cold Fluid
FIGURE 3.8.1 Matching of temperature glides. Hot fluid 3 has the best match with the cold
fluid.

Hot Fluid
Cold Fluid 2
Cold Fluid 1
FIGURE 3.8.2 Matching temperature glides. Cold fluids 1 and 2 leave nonlinear temperature
glides and pinch points can occur in the middle of the heat exchanger (Cold fluid 2) or in the
end (Cold fluid 1).
When the glides are parallel, i.e., they “match” as it is often termed, the entropy
production by the heat exchanger can be reduced to zero (in theory) by increasing
the heat exchanger area. When a pinch point exists, this is not possible any more.
When the heat exchanger area is increased, the approach temperature at the pinch
point becomes smaller but a large temperature difference continues to exist at the
other end of the heat exchanger. In the theoretical limit, for an infinitely large area,
the entropy production of this heat exchanger stays finite, even when the approach
temperature of the pinch point approaches zero. Thus, it is very important to strive
wherever possible for matching glides in heat exchanger design. With a nonlinear
glide, the pinch point can occur at any location within the heat exchanger. Figure
3.8.2 shows two examples with a concave and convex glide. For the concave case,
the pinch point occurs at the end of the heat exchanger; however, for the convex
case, the pinch point occurs somewhere in the middle. Its location can no longer be
controlled by selecting the thermal capacity alone. Also, the existence of this pinch
point cannot be observed when only inlet and outlet stream temperature are measured.
When refrigerant mixtures are used, a nonlinear glide can be thought of as caused
by two mixture constituents of significantly different latent heats. Figure 3.8.3
displays the latent heat of a two-component mixture over the mass fraction range.
The latent heat for component B is assumed to be significantly larger than that for
component A. Let us further assume that the fugacity of B is smaller than that of A
and that any effects of the heat of mixing are negligible. Thus, component A will
predominantly evaporate and the apparent latent heat for this portion of the evaporation
process will be dominated by the latent heat of A. This is indicated in Figure 3.8.3
with the latent heat of the mixture staying at levels similar to that of A. In this region,
a small amount of heat evaporates a relatively large amount of refrigerant. With the
accompanying change in composition, this accounts for a significant temperature
glide as shown in Figure 3.8.4, while the remaining liquid is evaporated with a
significantly higher latent heat.

Latent
Heat (q)
0 1.0
X
A B
FIGURE 3.8.3 Component A has a low latent heat, component B a high one. When the mass
fraction of A is high in the vapor phase, its latent heat dominated that of the mixture for a
wide range of x.
Hot Fluid
Mixture of A & B
FIGURE 3.8.4 A mixture with the constituents A, B of Figure 3.8.3 shows a nonlinear glide
with a pinch point in the middle of the heat exchanger.
During this first portion of the evaporating process, the remaining liquid phase
will be enriched in B only when the evaporation process approaches its end and the
remaining portion of B must evaporate as well with the latent heat of the mixture
approaching that of B. The curve of the latent heat in Figure 3.8.3 rises to the level
of the latent heat of B. In this portion of the evaporation process, the amount of heat
absorbed for a given mass fraction change is larger. The resulting temperature interval
is larger than before and the glide decreases in slope as shown in Figure 3.8.4. The
mixture AB has characteristics that produce a convex temperature glide with a pinch
point in the middle of the heat exchanger.
When the latent heat of A is much higher than that of B, the effects are reversed
and curves with the opposite behavior were generated. The result is a mixture with

a concave glide. Nonlinear glides have certain challenges and opportunities in heat
pump applications. When water or dry air is the heat transfer medium for an
evaporating or condensing mixture, the mixture should have a linear glide of equal
size for best glide matching when the refrigerant side pressure drop is accounted
for. When the heat transfer medium has a nonlinear glide on its own, as happens in
the case of dehumidification of air, the temperature glide of the refrigerant mixture
should match that of the air stream. Another example where a nonlinear glide is
welcome is for systems with two evaporators or two condensers that operate on
different temperature levels. A more detailed description of these is given in Chapter 5.
It should be noted that for best heat pump performance, the temperature glides
must match in both heat exchangers, the evaporator and condenser. The situation is
complicated by the fact that most systems require in the evaporator a certain degree
of superheat and in the condenser a certain degree of subcooling. These character-
istics add their own glide to that of the mixture two-phase range. Finally, a significant
superheat is also present in the condenser. This challenge is never met by any heat
transfer fluid and the designer is forced to find a suitable compromise.
3.9 METHODS FOR COMPARING THE PERFORMANCE

OF PURE AND MIXED REFRIGERANTS
Since mixtures are emerging as important substitutes, the heat pump designer is
confronted with the task of comparing fairly and conclusively the performance
potential of pure and mixed refrigerants in heat pumps. The following chapter points
out important considerations and relationships. The most important consideration is
the basis on which the comparison is made. Depending on this choice, the outcome
can vary greatly or even lead to contradictory results.
For example, the temperatures inside the two-phase regions of the condenser
and evaporator can be chosen as a basis. For pure fluids, this choice may be
acceptable since the saturation temperatures are well defined. However, when zeo-
tropic mixtures are used, this is not valid anymore and the choice of the proper
temperature for the sake of comparison is a matter of debate.
There are many different criteria that can be employed. From a user point of
view, the heat pump with the lowest life cycle cost may be of interest but it could
also be the one with the lowest operating or first cost. On the other hand, for an
engineer conducting an exploratory study, a focus on the temperatures internal to
the system may suffice for an initial estimate. Depending on the means and funds
at hand, comparisons can span this range of complexity with varying results. The
following is a list of basic assumptions on which comparisons are often based: life
cycle cost of heat pump, first cost of heat pump, operating cost of heat pump, some
heat exchanger area and some external fluid temperatures (i.e., chilled water) or
refrigerant temperatures.
Alternatively, a user might not only focus on the life cycle or operating cost of
a heat pump, but also on that of the complete system. For example, the first cost
of making heat available, such as the earth loop for a ground coupled heat pump
or the cooling water loop and cooling tower for a water chiller, is an important

Case A Case B
Tcond
Mixture Pure Refrigerant
Refrigerant Temperature
Tevap
Case C Case D
Refrigerant Flow
Tcond
Tevap
Cond Outlet Cond Inlet

Evap Inlet Evap Outlet
Position in Heat Exchanger
FIGURE 3.9.1 Four cases of refrigerant temperatures.
contribution. Most comparisons do not reach this level of sophistication because of

the effort and expense involved. Major changes in common practice are difficult and
expensive to implement.
The simplest criterion to base the comparison is to select the refrigerant tem-
peratures in the evaporator and condenser. Because of the influence of the glide, this
is where the confusion begins. Figure 3.9.1 shows four cases with the horizontal
lines representing the two-phase temperature levels of the pure fluids, the dashed
lines those of the mixture. An inspection of Figure 3.9.1 already reveals considerable
differences. While for all four options the temperature lift is constant for pure fluids,
it changes considerably for the mixture. Case A has the smallest average lift, while
case B exhibits the largest. Cases C and D represent compromises that seem to
produce average temperature lifts that are similar to those of the pure fluid. Since
the temperature lift is in good first approximation a measure for the work requirement
of the compressor, it is used here as a criterion to estimate the efficiency of the
cycles. Thus, Case A greatly favors mixtures with a small lift and resulting high
coefficient of performance, while Case B greatly disfavors mixtures. However, both
cases are not realistic for most applications. Cases C and D represent a compromise
but they can mask the performance potential of mixtures since they essentially force
the average temperature lift to be equal for all cases. These initial observations are
confirmed with more detailed calculations. McLinden and Radermacher (1987)
employed a simple thermodynamic model using a mixture of R22 and R114 as an
example.
Figure 3.9.2 shows the COP of pure R22, pure R114 and mixtures of both for
various compositions. The cycle is specified by the various pairs of refrigerant
temperatures of Figure 3.9.1. The saturation temperature of the pure components
was selected as –10 and 50˚C for the evaporator and condenser, respectively. Both
pure components have approximately the same COP of 4.1; however, the COPs of
the mixtures vary dramatically. For Case A, the mixture performs better than the

Case A
6
5
Heating COP Case D
4 Case C
3 Case B
2
0 0.2 0.4 0.6 0.8 1.0
Composition (mole fraction of R22)
FIGURE 3.9.2 Heating COP of R22/R114 mixtures.
pure components, showing a maximum COP at a composition of about 50 mol%

R114. For Case B, the COP of the mixture is always lower than that for the pure
components. This result confirms the expectations stated above. Thus, Case A rep-
resents a hypothetical maximum improvement that can be achieved with mixtures
as compared to pure refrigerants. Case B represents the highest performance degra-
dation. COP comparisons based on the internal (refrigerant) temperatures are not
conclusive and essentially worthless. However, the understanding of where the
temperature glides should be for beneficial effects is instructive. In heat exchangers
with counterflow heat exchangers and matched glides, the results are expected to be
between Case A and Case C. In crossflow heat exchangers with poorly matched
glides, the results will generally be between Case B and Case C.
It is a more productive approach to choose as the criterion for comparison the
external temperatures, i.e., the temperatures of the heat transfer fluids. As long as
these (and the flow rates) are constant, the heat pump performs the same duty and
any change in the COP due to change in working fluids is clearly an efficiency gain
or loss. However, when the external fluid temperatures (inlet and exit) are kept
constant, the average temperature lift can still be influenced by the approach tem-
peratures. To eliminate this uncertainty, the heat transfer area should be kept constant
as well. This has the advantage that the cost for the heat exchangers is also essentially
kept constant. As a consequence, this method approaches on first approximation a
comparison at constant first cost. It is assumed here that the compressor cost and
the heat transfer coefficients are the same for all fluids concerned; the latter is
generally not the case. Nevertheless, on the basis of constant heat transfer area and
coefficients and that the external temperatures are matched, the following observa-
tions can be made based on the assumption that the effects of superheating and
subcooling, nonlinearity of the glide and influence of the expansion valve are
neglected. It is further assumed that all heat exchangers are counterflow heat
exchangers.

The results of this study can be summarized as follows:
1. When the temperature glide of the refrigerant inside the heat exchanger
matches that of the external fluid stream, the potential COP improvement
is largest.
2. If the glide of the refrigerant is much smaller or much larger than that of
the external fluid, the COP is penalized.
3. The larger the glide (when refrigerant glide and external glide are
matched) and the smaller the lift, the higher the improvement in COP.
4. The theoretical limit for the improvement in COP is the doubling of the
value for a pure fluid (Case A in Figure 3.9.1). In this case, the temperature
of the refrigerant leaving the evaporator is the same as that of the refrig-
erant leaving the condenser. Any further increase in the evaporator outlet
temperature, or decrease in the condenser outlet temperature, would allow
for direct heat exchange between the respective external fluid streams and
eliminate the need for a heat pump in this range of the temperature glide.
5. Since the glide of a mixture varies with mass fraction, only certain mass
fractions lead to the best match and therefore performance improvement.
When a mixture has a large temperature glide and the application only a
narrow one, there may be two mixture mass fractions that match the glide:
a low mass fraction and a high mass fraction. At other mass fractions, the
performance could be reduced.
6. The capacity changes primarily with the vapor pressure of the refrigerant
at evaporator conditions. When mixtures have a large glide, the change in
capacity with mass fraction can be considerable as discussed in Chapter 7.
7. The highest performance improvement is gained when the glide in the
condenser and the evaporator are matched simultaneously.
3.10 SIMULATION OF THE VAPOR COMPRESSION CYCLE

This section introduces various modeling efforts for the vapor compression cycle.
Modeling of the vapor compression cycle is important in determining the potential
of alternative refrigerants and for designing the refrigerant cycle components and
system appropriately according to the thermophysical characteristics of refrigerant
mixtures since the experimental approach is too costly and time-consuming.
3.10.1 REFRIGERATION COMPONENT MODELS

Four components constitute a basic vapor compression cycle. Therefore, each basic
cycle model consists of four component models: a compressor model, an expansion
device model and two heat exchanger models. These component models serve as
the basic building blocks for the cycle model.
3.10.1.1 Heat Exchanger Model

In order to develop a high quality cycle simulation for a vapor compression system,
an accurate heat exchanger model is essential. The heat exchanger model significantly

impacts not only the heat transferred, but also the amount of refrigerant in the system.
In general there are two types of heat exchanger models: One is a relatively simple
UA model and the other is a detailed model based on distributed parameter heat
exchanger simulation that solves the continuity, species, momentum and energy
equations simultaneously for air (or water) to refrigerant heat exchangers while using
local heat transfer and pressure drop correlations.
Prominent among the previous work on this subject is the tube-by-tube analysis
developed by Domanski (1989 and 1995). In this analysis, a wet (moisture from air
conditioning on the outside surface) or dry evaporator was modeled by assuming
the air passes directly from one tube to another. The heat and mass transfer of each
tube was evaluated based on its own air and refrigerant inlet states; this allowed for
investigation of air maldistribution. The simulation, restricted to pure refrigerants,
was experimentally verified for wet coils and found to predict the overall capacity
within –8.8 to +23.3% (Chawalowski et al., 1989).
Using the work by Domanski, Conde and Sutter (1992) developed a similar
simulation with several modifications. One of the improvements included the ability
to determine the refrigerant inventory within the evaporator. This code was part of
an overall steady state cycle simulation and was experimentally verified with R22.
The verification showed that the simulation frequently overpredicted the capacity
by more than 10%.
Oskarsson et al. developed three steady state models for dry, wet and frosted
evaporators. All of the models assumed that the entire heat exchanger could be
simulated with one equivalent tube in crossflow. Furthermore, these models were
developed for pure refrigerants. One of the models divided the evaporator into three
different regions: the two-phase region, the transitional region and the superheated
region. The most complex model divided the heat exchanger into finite elements,
while the simplest model was parametric and required one of the other models to
generate constants for it. The three-region model was experimentally verified and
found to predict the capacity of a dry coil between –17.7 and +11.3%. Furthermore,
the finite element model agreed with the three regions model within 2%.
Nyers has developed a transient evaporator model (Nyers, 1994). This model
was developed for air to pure refrigerant applications. This model was fully distrib-
uted and simultaneously solved the continuity, momentum and energy equations but
was not compared to any transient or steady state experimental data.
Judge and Radermacher (1997) developed a finite element transient and steady
state model that was verified experimentally within 8%. The authors used this model
to quantify the effects of heat exchange geometry on the performance of R407C.
For the conventional shell-and-tube heat exchangers, Hwang and Radermacher
(1998) developed a water-to-refrigerant evaporator and condenser models that
divided the heat exchanger into finite elements. These models are verified with
experimental data for R22 and CO2: a 5% deviation for the evaporator model and
a 7% deviation for the condenser model were reported.
UA Model
When analyzing the heat exchanger, either log-mean-temperature-difference
(LMTD) or the effectiveness-NTU (number of transfer units) method can be used.

In this section, only the LMTD model is explained. If the reader is interested in the
effectiveness-NTU method, the detailed explanation and examples can be found
from Incropera and DeWitt (1990).
In the UA model, the heat exchanger performance is defined as Equation 3.19,
Q = UA × LMTD (3.19)
where
U = overall heat transfer coefficient
A = total heat transfer area
LMTD = log-mean-temperature-difference
In this model, three parameters in Equation 3.19 are given and the other variable
is calculated by Equation 3.19. If the heat exchanger geometry (A) and the opera-
tional conditions (U and ∆T) are given, the heat exchanger performance (Q) is
calculated. On the other hand, if the target performance (Q) is given, only one
parameter among the heat exchanger geometry (A) and the operational conditions
(U and ∆T) is calculated while the other two parameters are given.
Applying the UA model for each flow regime can further advance the UA model.
An evaporator should be divided into two-phase and superheated regions. A con-
denser should be divided into superheated, two-phase and subcooled regions. The
total heat exchanged is then the sum of the heat exchanged at each region, as shown
in Equation 3.20,
Q= ∑ Q = ∑U A × LMTD
i i i i (3.20)
where
Ui = overall heat transfer coefficient for each segment
Ai = total heat transfer area for each segment
LMTDi = log-mean-temperature-difference for each segment
When applying the LMTD, some considerations must be accounted. First, the LMTD
is designed for counterflow heat exchange configuration. However, it can be used
for many different HX (heat exchanger) geometries by using the correction factor
(CF) as shown in Equation 3.21,
∆Tin − ∆Tout
LMTD = CF ×
( )
(3.21)
ln ∆Tin / ∆Tout
where
CF = correction factor for heat exchanger geometry (examples are given in
Figure 3.10.1)
∆Tin = temperature difference between hot fluid inlet and cold fluid outlet
(Thf,in – Tcf,out)
∆Tout = temperature difference between hot fluid outlet and cold fluid inlet
(Thf,out – Tcf,in)

1.1
p/q=0.2
1.0
0.4
Correction Factor (CF)

0.9
0.6
0.8
0.8
0.7
1.5
0.6
2
0.5
3
0.4 4
0.3
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
q
FIGURE 3.10.1 LMTD correction factor for single pass crossflow heat exchanger (one fluid
mixed, other unmixed).
When one fluid undergoes phase change or two fluids have a very similar heat
capacity, then CF = 1. A correction factor for single pass crossflow HX, one fluid
mixed, other unmixed, as is the case for most of the air-to-refrigerant heat exchan-
gers, is available from Bowman (1940) as shown in Equation 3.22,
p− q
CF = r /r0 = r
( )
1− q
(3.22)
ln 1− p
Thf ,in − Thf ,out

where p =
Thf ,in − Tcf ,in
Tcf ,out − Tcf ,iin

q=
Thf ,in − Tcf ,in
Figure 3.10.1 shows the result of this correlation.

When applying the LMTD method for zeotropic mixtures having a nonlinear
temperature glide during phase change, segmentation of the two-phase region is
desirable to simulate the zeotropic mixture’s phase-change correctly. When applying
the LMTD method for multiphase region heat exchangers, the overall temperature
difference can be defined in different ways. In Cycle 7, McLinden (1987) introduced
the superposition LMTD as defined in Equation 3.23,
LMTDhx = ∑ f LMTD
i
i i (3.23)
where
LMTDhx = LMTD for overall heat exchanger
fi = heat transfer fraction for individual phase zone (Qi /Qhx)
LMTDi = LMTD for individual phase zone

By assuming the constant heat transfer coefficient (U) for all phases, Rice and
Sand (1990) and Domanski and McLinden (1990) introduced the harmonic weighted
LMTD as defined in Equation 3.24,
1
LMTDhx
= ∑ LMTD
i
fi
i
(3.24)
Detailed Heat Exchanger Models

Two heat exchanger models for the air-to-refrigerant (pure fluids and mixtures) heat
exchangers, applicable to both pure fluids and mixtures, are introduced based on
Judge and Radermacher’s (1997) work: one for simulating the performance of the
evaporator with two-phase boiling and single-phase heat transfer, one for simulating
the performance of the condenser with two-phase condensation and single-phase
heat transfer. It is assumed that the conventional finned tube heat exchangers are
used. These models are distributed as parameter heat exchanger models. In this
model, many existing heat transfer correlations were compared with the experimental
data. As the boiling heat transfer correlations, Gungor and Winterton (1986), Shah
(1982), Kandlikar (1991), Chen (1966) and Jung et al. (1989a) correlations were
examined. As the condensation correlations, Tandon et al. (1986), Chen et al. (1987),
Traviss et al. (1973), Shah (1979) and Dobson et al. (1994) correlations were
examined. The authors recommended two correlations among the examined corre-
lations: Jung’s correlation predicted the evaporator capacity with –5 to +4% and
Dobson’s correlation predicted the condenser capacity within –3 to +7%. The
increased deviation in condensation relative to evaporation occurred due to the lack
of the condensation heat transfer correlations that were generally applicable for any
mixture. However, the inaccuracy of the refrigerant side heat transfer coefficient is
less significant than the airside. Details of boiling and condensation heat transfer
correlations are introduced later in Chapter 8.
These heat exchanger models determine cooling or heating capacity by assuming
two cycle parameters (evaporating pressure and condensing pressure) and calculating
the pressure drop in the heat exchanger. Moreover, these models calculate required
heat exchanger areas by calculating heat transfer coefficients and mean temperature
difference between refrigerants and air. When the difference between the calculated
heat exchanger area and the given heat exchanger area becomes less than the
converging criteria, all cycle parameters (capacity, COP and outlet conditions) are
finalized.
Air-Side Heat Transfer Coefficient
The airside is assumed to be incompressible and fully developed hydraulically. The
relevant conservation equations are continuity, momentum and energy equations.
Most air-side heat transfer correlations for different fin geometries are developed
for both a single tube and a bank of tubes in crossflow. Webb (1990) suggested the
air-side heat transfer correlation for heat exchangers with flat and wavy plate fins
on a staggered array of circular tubes as shown in Equations 3.25 and 3.26.

For flat fin,
Nu a = 0.4 Gz 0.73 (s/D c )−0.23N 0.23

R for Gz ≤ 25
(3.25)
Nu a = 0.53 Gz 0.62 (s/D c )−0.23N 0.31
R for Gz > 25
For wavy fin,
Nu a = 0.5 Gz 0.86 (Pt /D c )0.11(s/D c )−0.09 (Sd /Pl )0.12 (2Sp /Pl )−0.34 for Gz ≤ 25
(3.26)
Nua = 0.83 Gz 0.76 (Pt /Dc )0.13 (s/Dc )−0.16 (Sd /Pl )0.25 (2Sp /Pl )−0.43 for Gz > 25
where
Gz = Graetz number (RePrDH/L)
s = space between fins (fin pitch – fin thickness)
Dc = fin collar outside diameter
Sd = peak-to-vallet wave depth
Pl = longitudinal tube pitch
Sp = one-half wave length
NR = number of tube rows
Refrigerant-Side Heat Transfer Coefficient

A correlation is required for the local refrigerant-side heat transfer coefficients. As
for the single-phase heat transfer coefficients, Gnielinski’s (1976) correlation shown
in Equation 3.27 is used for 2300 ≤ Re ≤ 5 × 106.
Nu =
(
( f /8) Re − 1000 Pr )
( Pr )
(3.27)
1 + 12.7( f /8) 0.5 2/ 3
−1
where
f = (0.79 ln(Re) – 1.64)–2
As for the two-phase heat transfer coefficients, many correlations are available.
In this section, one preferred boiling and one condensation correlation are intro-
duced, which provided the smallest error with experimental data. Details of boiling
heat transfer correlations are described in Section 8.3; details of condensation heat
transfer correlations are described in Section 8.6.
Jung et al. (1989b) developed the following flow boiling correlation for horizontal
tubes for the binary mixtures R22/R114 and R12/R152a as shown in Equation 3.28,
h = Cme Fhl + S /Cun h pool (3.28)

where
hl = heat transfer coefficient for the liquid phase flowing alone
F = forced convection enhancement parameter
where
F = 2.37 (0.29 + 1/Xtt)0.85
S = forced convection suppression parameter
where
S = 4048 Xtt1.22 BO1.13 for Xtt < 1
S = 2 – 0.1 Xtt–0.28 BO–0.33 for 1 < Xtt < 5
Cme = 1 – 0.35 |Xv – Xl|1.56
where
Xl = liquid phase mass fraction
Xv = vapor phase mass fraction
Cun = |1 + (b2 + b3)(1 + b4)| × (1 + b5)
hpool = pool boiling heat transfer coefficient
where
hpool = hi /Cun
hi = ha hb /(hb Xl + ha Xv)
ha hb = pool boiling heat transfer coefficient of pure refrigerants a and b given
by Stephan and Abdelsalam’s (1980) correlation
b2 = (1 – Xl) ln |(1.01 – Xl)/(1.01 – Xv)| + Xl ln (Xl /Xv) + |Xl – Xv|1.5
b3 = 0 for Xl µ 0.01
b3 = (Xl /Xv)0.1 – 1 for Xl < 0.01
b4 = 152 (P/Pca)3.9
b5 = 0.92 |Xl – Xv|0.001 + (P/Pca)0.66
Xl /Xv = 1 for Xl = Xv = 0
where
Pca = critical pressure of more volatile component
Sweeney (1996) and Sweeney and Chato (1996) correlated Kenney et al.’s (1994)
data for R407C in a smooth tube using Dobson’s correlations,
0.3
 G 
h = 0.7 
 300 
 kl
 D
0.8 0.4
( )
−0.89 
 0.023 Rel Prl 1 + 2.22 Xtt  for annual flow regime (3.29)


 0.23 Re 0v .12  Ga Prl  

0.3
 G 
h=  + (1 − θl /π) Nu f  for wavy flow regime (3.30)
 300  0.58 
 1 + 1.11X tt  Jal 


where
Nu f = 0.0195 Rel0.8 Prl0.4 φl ( X tt )
where
C1
φl ( X tt ) = 1.376 +
X tt c2
where
c1 = 4.12 + 0.48 Frl – 1.564 Frl2, c2 = 4.12 + 0.48 Frl – 1.564 Frl2, for 0 < Frl ≤ 0.7
c1 = 7.242, c2 = 1.655 for Frl > 0.7
where
Frl = liquid Froude number
θl = angle subtended from the top of the tube to the liquid level
θl arccos(2α − 1)
1− ≅ by Jaster and Kosky (1976)
π π
Tubes and Fins

When the segmentation technique is applied for the heat exchanger models, it is
assumed that each segment is at one temperature and that the axial conduction is
negligible.
Two heat transfer resistances associated with the tube and fin are the resistance
due to the tube itself and the resistance due to the contact between the fin and the
tube. The contact resistance is estimated from Sheffield’s correlation (Sheffield et al.,
1989). The fin efficiency (ηf ) and overall surface efficiency (ηo) are calculated using
the method described by Incropera and Dewitt (1990) as shown in Equations 3.31
and 3.32,
tanh(mL )
ηf = (3.31)
mL
where
m = (hP/kAc)0.5
h = air-side heat transfer coefficient
P = fin perimeter
k = fin thermal conductivity

Ac = fin cross-sectional area
L = fin height
Af
ηo = 1 − (1 − η f ) (3.32)
At
where
Af = fin surface area
At = total surface area (fin surface area + fin base area)
Overall Heat Transfer Coefficient

The overall heat transfer coefficient (U) is calculated based on a distributed parameter
heat exchanger simulation that calculates a local overall heat transfer coefficient
from Equation 3.33 using the air-side and refrigerant-side heat transfer coefficients.
1
U= (3.33)
Ao 1 Ao ln(ro /ri ) 1
+ +
Ai hr 2πkL ηo ha
where
hr = refrigerant-side heat transfer coefficient
ha = air-side heat transfer coefficient
ro = tube outside radius
ri = tube inside radius
Ao = tube outside surface area
Ai = tube inside surface area
k = thermal conductivity of tube
L = tube length
Refrigerant-side Pressure Drop

Refrigerant-side pressure drop in single-phase regions (superheated gas and sub-
cooled liquid) is calculated by using the Blasius friction factor for turbulent in-tube
flow (Blasius, 1913) as shown in Equation 3.34,
0.0791
f= for 2.1 × 10 3 < Re < 10 5 (3.34)
Re 0.25
As for the two-phase pressure drop, many correlations are available. In this
section, the most preferred boiling pressure drop and condensation pressure drop
correlations are introduced, having the smallest error with experimental data. Details
of boiling pressure drop correlations are described in Section 8.4; details of conden-
sation pressure drop correlations are described in Section 8.7.

Jung and Radermacher (1989) studied the boiling pressure drop of R12, R22,
R114, R152a and R12/R152a. The authors suggested a modified version of Marti-
nelli-Nelson correlation as shown in Equation 3.35,
2 f f 0G 2 L  1 
∫
x2
∆Ptp =  φtp2 dx  (3.35)
Dρl  ∆x x1 
where
ffo = 0.046 Re–0.2
G = mass flux
D = tube diameter
ρl = liquid density
φtp2 = 30.78 x1.323 (1 − x )0.477 Pr−0.7232
where
Pr = reduced pressure (P/Pc)
Sami et al. (1992) suggested using the Lockhart-Martinelli parameters to calcu-

late the frictional pressure gradient during the condensation process based on their
measurement on R22/R152a/R114 and R22/R152a/R124 in an enhanced tube. The
suggested correlation is shown in Equations 3.36 through 3.40. They correlated the
friction factor using the form of Blasius as shown in Equation 3.41,
∆P = ∆Pf + ∆Pm (3.36)
where
∆P = total two-phase pressure drop
∆Pf = frictional pressure drop
∆Pm = pressure drop due to the momentum change
G2   x 2  ρ  (1 − x )2   x 2  ρ  (1 − x )2  
∆Pm =    +  −  + 
l l
(3.37)
ρl α  ρ  (1 − α ) α  ρ  (1 − α ) 1 
  v 2  v
where
G = mass flux
ρv = vapor density
x = vapor quality
α = void friction

−1
   x ρl /ρv + 0.4(1 − x )   
( )
0.5
  ρv   1 − x  
α = 1 +      0.4 + 0.6    (3.38)
  ρl   x
 

x + 0 .4 (1 − x )   
 
(
∆Pf /∆z = ∆P /∆z v Φ 2v ) (3.39)
where
Φv = Lockhart-Martinelli parameter
 ∆P  2 fvG 2 x 2
 ∆z  = (3.40)
v
Dρv
where
∆Pv = vapor flow pressure drop
D = tube diameter
fv = frictional coefficient considering two-phase flow as vapor flow
f = 0.6 Re −0.21 (3.41)
To investigate the benefit of temperature glide of R407C, different heat exchanger

geometries, crossflow, parallel flow and counter flow were examined. The results
are shown in Tables 3.1 and 3.2. R407C showed capacity degradation in the parallel
flow heat exchange configuration and capacity improvement in the counter flow heat
exchange configuration over R22. Performance penalty of R407C was about 4 to
5% for the parallel flow and performance improvement of R407C was about 3 to 4%
TABLE 3.1
Effect of Heat Exchanger Geometry in Cooling Mode
Heat Exchanger Condenser Capacity Evaporator Capacity

Geometry R22 R407C R22 R407C
Crossflow 100 100 100 100

Parallel flow 96 92 98 96
Counter flow 103 103 101 103
Air and refrigerant boundary conditions are based on experimental

values. The airside heat transfer coefficient, area and fin efficiency are
based on the crossflow values.
Source: Judge and Radermacher, 1997.

TABLE 3.2
Effect of Heat Exchanger Geometry in Heating Mode
Heat Exchanger Condenser Capacity Evaporator Capacity

Geometry R22 R407C R22 R407C
Crossflow 100 100 100 100

Parallel flow 96 95 99 98
Counter flow 103 104 100 100
Air and refrigerant boundary conditions are based on experimental

values. The airside heat transfer coefficient, area and fin efficiency are
based on the crossflow values.
Source: Judge and Radermacher, 1997.
for the counter flow as compared to the crossflow configuration. It should be noted
that the penalty of parallel flow is a little bit more severe than the benefit of counter
flow since the parallel flow encountered a pinch point.
3.10.1.2 Compressor Model
The compressor is the heart of the vapor compression cycle and there are many levels
of complexity among the compressor models in the literature. In general, compressor
models are classified into four versions: efficiency model, map-based model, lumped
parameter model and distributed parameter model. There are six representative com-
pressor efficiencies: overall isentropic efficiency (ηoverall,isen), volumetric efficiency
(ηvol), motor efficiency (ηmot), mechanical efficiency (ηmec), isentropic efficiency (ηisen)
and suction gas superheating efficiency (ηsuperheat) (Shaffer and Lee, 1976). The def-
inition of these six efficiencies is as follows:
ideal isentropic compression work (from shell inlet to outlet)

ηoverall ,isen =
actual mootor power
actual refrigerant mass flow rate
ηvol =
ideal refrigerant mass flow rate
shaft power
ηmoot =
actual motor power
(3.42)
indicated power
ηmec =
shaft power
ideal isentropic compression work

ηisen =
indicated power
ideal isentropic compression work (from shell inlet to outlet)
ηsupeerheat =
ideal isentropiic compression work (from suction port to outlet)

where
indicated power = work delivered to the gas
An isentropic analysis model is the simplest model and is independent of the physical
characteristics of compressors and various types of refrigerants. Typically, two
efficiencies, isentropic and volumetric efficiency, are given as inputs in this model.
These two efficiencies can be directly obtained from experimental data or varied as
a design parameter.
The second model is a polytropic analysis model. Some investigators prefer to
use the polytropic efficiency instead of the isentropic efficiency. The polytropic
efficiency is defined by Equation 3.43,
polytropic compression work

η pol = (3.43)
(refrigerannt enthalpy change × mass flow rate)
where the polytropic compression work (Wp) is defined by Equation 3.44,
 n −1 
n   Pdis  n 1
Wp = PsucVsuc   − (3.44)
n -1  P  
 suc 
where the polytropic index (n) is defined by Equation 3.45,
n − 1 ( γ − 1) /η pol
= (3.45)
n γ
This compressor model is attractive because it accounts for several nonidealities

in a very simple form and is demonstrated by Welsby and Domanski’s general
compressor model for an air-conditioning and heat pump simulation (Welsby, 1988;
Domanski and McLinden, 1992). In this model, the compressor rotates at a constant
RPM and does not account for volumetric efficiency. In other words, the volume
flow rate though the compressor is constant; the compressor power and discharge
state are determined by assuming polytropic compression with a constant polytropic
index. The goal of this polytropic analysis can be broken down into two objectives:
one is to determine the refrigerant flow rate and the other is to determine the outlet
state. The refrigerant flow rate is obtained by multiplying the volumetric efficiency
with the theoretical maximum mass flow rate. The volumetric efficiency accounts
for re-expansion of the refrigerant in the clearance volume and the density change
of the refrigerant prior to entering the compressor.
A map-based model is one of the most frequently used approaches in industry.
In this model, the compressor performance is modeled by curve fitting steady state
experimental data. One curve fit method is to define the mass flow rate, discharge
state and compressor power as functions of the suction conditions and pressure ratio

(Murphy and Goldschmidt, 1985). Although the map-based model is very accurate
for a given fluid at steady state, it is not generally applicable to refrigerants and
compressors other than the ones upon which it was based. Compressor manufacturers
provide coefficients based on ARI Standards for the positive displacement compres-
sor, ARI Standards 520 (1997) and 540 (1999). Revised ARI Standard 540 (1999)
used suction- and discharge-dew point temperatures as its test conditions while
AREP (1993) and Rice (1993) used mean temperature of bubble and dew temperature
for the evaporating and condensing temperatures. Pure refrigerants, azeotropic mix-
tures and near-azeotropic mixtures are not affected by dew point- and mean tem-
perature-approaches. However, zeotropic mixtures, especially having a large tem-
perature glide, can show differences when these two approaches are compared. Since
mean evaporating and condensing temperatures of zeotropic mixtures are higher and
lower than dew temperatures at the suction and discharge, respectively, the dew point
approach will result in higher COP due to the reduced pressure ratio than the mean
temperature approach.
The most complex compressor model is a distributed parameter compressor
model. In this model the complete set of multidimensional energy, momentum and
continuity equations is somewhat simplified and solved. MacArthur developed the
distributed parameter model that deals with seven different state points (MacArthur,
1984). The compression process is assumed to be polytropic. Heat transfer between
different compressor components is accounted for by utilizing constant heat transfer
coefficients, as is the effect of thermal storage. Judge (1996) developed a distributed
parameter compressor model that accounts for valve dynamics and heat exchange
between various components of the reciprocating compressor. Other studies using
this type of model include: Ng et al. (1976), Recktenwald et al. (1986), Perez-Segarra
et al. (1994) and Lio et al. (1994).
From this literature review, it is clear that there is a wide range of methods
available for modeling compressors. The simple method, the efficiency model, is
most convenient for design point analysis but is of less accuracy over a range of
operating conditions. However, this method is a good approach for parametric
studies. The distributed parameter model provides better accuracy but needs larger
computing time.
3.10.1.3 Expansion Device Model
The purpose of the expansion device is to reduce the pressure of the refrigerant. The
temperature of the refrigerant during expansion is also reduced so that the refrigerant
can absorb heat in the evaporator. The simplest expansion device model is a ther-
modynamic expansion model that assumes an isenthalpic expansion with negligible
heat loss. The expansion device inlet enthalpy then equals the outlet enthalpy and
this model can avoid any hardware dependence.
The four common expansion devices are capillary tubes, short tube orifices
(STs), thermostatic expansion valves (TEVs) and metering valves. In actual systems,
the capacity and operating mode determine the preferred expansion device. Capillary
tubes are used for small capacity cooling applications; STs are used for medium
capacity cooling applications; TEVs are used for larger capacity cooling and heating

applications. Among the expansion devices, the ST garners attention recently because
of its simplicity, low cost and serviceability.
Short Tube Models
Though the geometry of the STs is very simple, the expansion process within the
STs is so complex that it is difficult to accurately correlate experimental data from
various refrigerants and boundary conditions. Three modeling efforts are introduced
as follows:
Mei (1988) developed a ST model based on his experimental data with R22. He
concluded that the degree of upstream subcooling and the pressure difference were
the major parameters of STs. He then suggested using a general orifice type model
but the orifice constant should be a function of those two parameters. Mei reported
that his correlation matched experimental data 3 and 4% in average for STs opening
and length, respectively.
Aaron and Domanski (1990) developed a ST model based on their experimental
data with R22. In their research, they found that the mass flow rate varied only 3 to
8% depending on downstream pressure in “choked” flow condition. The second
finding was that the mass flow rate depended upon the degree of subcooling: the
mass flow rate increased approximately 23% when the subcooling increased by
8.3˚C. They also reported that doubling the length of the ST reduced the mass flow
rate by 5% and inlet chamfering increased the mass flow rate by 5 to 25%, while
the exit chamfering had no impact on the flow rate. Based on the orifice equation
(Equation 3.46), they modeled the ST:
m = Cc Ac 2ρ( P1 − P2 ) (3.46)
where
Cc = ST chamfer coefficient
Ac = ST cross-sectional flow area
ρ = density of upstream fluid entering ST
P1 = upstream pressure
P2 = downstream pressure
Kuehl and Goldschmidt (1992) and Kim and O’Neal (1993 and 1994a) modified
the P2 of the form of the Aaron’s equation to correlate their data. Kornhauser (1993)
developed a more physically based model with Aaron’s experimental data by con-
sidering the metastable conditions occurring within the ST. However, this model is
applicable only to “choked” flow regions.
Since the correlations developed by Aaron, Kuehl and Kim were based on R22,
their correlations must be compared to experimental data with mixtures. Judge
(1996) compared his experimental data for R22 and R407C with Aaron and Kim’s
correlations. He reported that Aaron’s model predicted the low side pressure of R22
and R407C within 6 and 11% errors, respectively. He also reported that Kim’s model
had errors about twice as large as those of Aaron’s when it was compared with R22
experimental data.

Most recently, Payne and O’Neal (1998 and 1999) investigated mass flow char-
acteristics of R407C and R410A with and without POE oil through ST orifices 12.7,
19.1 and 25.4 mm in length with diameters of 1.09, 1.34, 1.71 and 1.94 mm. Payne
and O’Neal then fitted their data to a previously developed semi-empirical model
by Kim and O’Neal (1994a and 1994b), essentially the same form as Equation 3.46.
Payne and O’Neal’s correlation for R407C and R410A can handle two-phase inlet
conditions as shown in Equation 3.47. The effects of oil on the refrigerant mass flow
rate was reflected in the two-phase quality correction factor (Ctp) and adjusted down
stream pressure (P2a),
m = Ctp Acs 2 γ cρ( P1 − P2a ) (3.47)
where
m = mass flow rate [kg/s]
Ctp = two-phase quality correction factor
(Ctp = 1 for single phase; use Equation 3.48 for two-phase)
γc = constant (Table 3.3)
ρ = density of upstream fluid entering ST [kg/m3]
P1 = upstream pressure [kPa]
P2a = adjusted downstream pressure [kPa] (Equation 3.49)
{( )( )}
−1
C tp = 1 + a1x1 1 + a2 LD a3Y a4 Ln ( LD) (3.48)
where
LD = L/D
L = length of ST [mm]
D = ST diameter [mm]
a1, a2, a3, a4 = constant (Table 3.4)
0.5
x ρ 
Y= 1  l
1 − x1  ρv 
where
x1 = upstream vapor quality
ρl = saturated liquid density at upstream pressure
ρv = saturated vapor density at upstream pressure
{
P2a = Psat b1 + b2 PRAb3 LD b4 SUBC b 5 + b6 PRAb7 +
(3.49)
b8 exp(b9 DR × LDb10 ) + b11EVAP }

TABLE 3.3
Critical Parameters for Equation (3.47)
Critical Parameter R407C R410A
Pc 4619.14 kPa 4949.65 kPa

Tc 359.89 K 345.65 K
γc 1.2960 × 1010 kg/kPa-h2-m 1.2960 × 1010 kg/kPa-h2-m
Source: Payne & O’Neal, 1998; Payne and O’Neal, 1999.
TABLE 3.4
Coefficients of Correction Factors for Equations (3.48) and (3.49)
R407C R410A
Coefficients Pure 1.1% POE Oil Pure 2.2% POE Oil
A1 –4.45974577 –4.34974577 3.693038038 1.427618112

A2 10.6946713 10.45457121 0.120175996 0.530751112
A3 –0.55303036 –0.663120121 0.194241638 –0.365456266
A4 0.39429366 0.323273661 0.022577667 0.018669938
B1 0.963034325 0.980538238 0.874805831 1.050104183
B2 4.286408416 4.957604391 3.131470913 6.305986547
B3 –0.278235435 –0.309919995 –0.214726407 0.099138818
B4 –0.043090943 –0.116219951 0.083394737 –0.045626106
B5 0.916226528 0.906610038 0.901559277 0.958459297
B6 0.071794702 0.227476573 –0.020574536 –0.254071783
B7 0.499098698 0.186773583 0.944446846 0.137198955
B8 –0.208417565 –0.398196082 –0.418400083 –0.276516186
B9 –0.034680678 –0.030711793 –0.025322802 –0.014589768
B10 1.844061084 1.587754176 2.33507746 2.5121908
B11 –0.09123591 –0.134132834 0.068890172 0.13087558
Source: Payne & O’Neal, 1998; Payne and O’Neal, 1999.
where
Psat = saturated liquid pressure corresponding to upstream temperature [kPa]
PRA = P1/Pc
DR = D/1.524
SUBC = (Tsat – T1)/Tc
EVAP = (Pc – P2)/Pc
b1 through b10 = constants (Table 3.4)
3.10.1.4 Refrigerant Mixture Properties
The requirements for representation of mixture properties can be satisfied by the

REFPROP Version 5 refrigerant properties database that calculates the thermophysical

TABLE 3.5
Equations of State Available in REFPROP
Equation of State Applicable Fluids Source
Carling-Starling-DeSantis (CSD) All of the pure and mixture fluids DeSantis (1976)
except ammonia
Modified Bennedict-Webb-Rubin 13 fluids (R32, R123, R124, R125, Bennedict, Webb and
(MBWR) R134a, R143A, R152A, R290, Rubin, (1940)
R600, R600A, N-C5, I-C5, R236fa)
Extended corresponding states Thermodynamic properties of pure Huber and Ely (1992)
(ECS) and mixture fluids without an Huber et al. (1992)
MBWR EOS (Equation of State)
and transport properties of all fluids
except R134a
Haar-Gallagher (HG) Ammonia Haar and Gallagher (1978)
Source: Huber et al., 1996.
properties of 43 pure fluids and their mixtures of up to five components (Huber

et al., 1996). REFPROP uses four separate models to calculate thermodynamic
properties of pure fluids as shown in Table 3.5.
Among the above equations of state, the ECS model is adapted for the calculation
of R22 properties because only CSD and ECS models are available for R22 and the
ECS model represents the vapor pressure and saturated liquid density to nearly the
uncertainty in experimental data within 0.6%, while the CSD model exhibits sys-
tematic deviations that increase as the critical point is approached (McLinden et al.,
1993). Uncertainties of transport properties are 10% for thermal conductivity and
15% for viscosity (Huber et al., 1996).
As for the reference state for enthalpy and entropy, the REFPROP database
offers three options. Among these, the ASHRAE option is chosen as a convention
in this field because it has zero enthalpy and entropy for saturated liquid at –40˚C.
REFPROP Version 6 is available now with increased accuracy formulations for both
pure and mixed refrigerants.
3.10.2 CYCLE MODELS

3.10.2.1 NIST Model: Cycle 7 and Cycle 11
As a serious effort to evaluate the performance of possible alternatives for the existing
refrigerants, researchers at NIST developed several cycle simulation models. Ini-
tially, McLinden (1987) developed a cycle model Cycle 7 which consists of seven
cycle state points as shown in Figure 3.10.2(a).
Cycle 7 then evolved by adding a suction-line heat exchanger and by improving
the compressor model, resulting in Cycle 11 which consists of eleven state points
as shown in Figure 3.10.2(b) (Domanski and McLinden, 1992).

3
4
Temperature
7
6
Entropy
(a)
5
6
Temperature
7
8
2
1
11
10
9
Entropy
(b)
FIGURE 3.10.2 State points of two cycle models. (a) State points of Cycle 7. (b) State points
of Cycle 11.
Eleven state points shown in Figure 3.10.2(b) are:

point 1 Suction line outlet, compressor shell inlet
point 2 Refrigerant state in the cylinder before the compression process
point 3 Refrigerant state in the cylinder after the compression process
point 4 Compressor shell outlet, condenser inlet
point 5 Saturated vapor refrigerant state in the condenser

point 6 Saturated liquid refrigerant state in the condenser

point 7 Condenser outlet, liquid line inlet
point 8 Liquid line outlet, expansion device inlet
point 9 Expansion device outlet, evaporator inlet
point 10 Saturated vapor refrigerant state in the evaporator
point 11 Evaporator outlet, suction line inlet
Other investigators have used Cycle 11 to compare the potential performance

of possible replacement refrigerants for R22 (Pannock and Didion, 1991; Domanski
and Didion, 1993).
3.10.2.2 Binary Mixture Performance Analysis
Pannock and Didion (1991) used Cycle 11 to find the most promising binary zeotropic
mixtures for residential heat pump applications with the following hydrofluorocarbons
(HFCs): R23, R32, R125, R134a, R143a and R152a. In their work, the following
assumptions were used:
• Isenthalpic expansion.
• Suction-line heat exchanger (SLHX) was not implemented.
• Fixed cycle parameters such as the compressor speed, refrigerant pressure
drops in the heat exchangers, polytropic compressor efficiency, degree of
subcooling at the condenser outlet, degree of superheating at the com-
pressor outlet and compressor cylinder inlet and outlet pressure drop and
heat transfer coefficients.
• Heat transfer fluid inlet and outlet temperatures are based on four cooling
test conditions, A, B, C, and D, as specified in ASHRAE Standard 116
(1995).
• Heat transfer fluid is water/glycol mixture. Temperature change of the
heat transfer fluid is set to 12.2 and 8.2°C for the evaporator and condenser,
respectively, to simulate evaporator- and condenser-air flow rate 400 CFM
and 800 CFM, respectively.
After a series of simulation runs for binary mixtures of the above pure refrigerants,
the two most promising mixtures, R32/R152a and R134a/R152a, were selected
among 15 binary mixtures (R23/R32, R23/R125, R23/R143a, R23/R134a,
R23/R152a, R32/R125, R32/R143a, R32/R134a, R32/R152a, R125/R143a,
R125/R134a, R125/R152a, R143a/R134a, R143a/R152a and R134a/R152a). The
R32/R152a mixture showed the best performance. The second and third best per-
forming mixtures were R32/R134a and R125/R134a, respectively.
Figures 3.10.3 and 3.10.4 show the relative volumetric capacity and COP versus
the R32 mass fraction to those of R22. Due to the large number of graphs generated
by this study, the authors refrained from appending all diagrams and restricted
themselves to the best performing mixtures: R32/R152a and R32/R134a. The volu-
metric capacity of R32/R152a reached that of R22 at 37 and 44% of R32 mass
fraction for cooling and heating, respectively. The maximum COP of R32/R152a for
cooling and heating was reached at about 40 to 50% of R32 mass fraction. The R32

60
R32/R134a
Vol. Capacity Improvement over R22 [%]

50
R32/R152a
40
30
20
10
0
−10
−20
−30
−40
−50
0 0.2 0.4 0.6 0.8 1.0
R32 Mass Fraction
(a)
20
15
COP Improvement over R22 [%]
R32/R152a
10
R32/R134a
5
−5
0 0.2 0.4 0.6 0.8 1.0
R32 Mass Fraction
(b)
FIGURE 3.10.3 Performance of R32/R152a and R32/R134a at ASHRAE Cooling A condi-

tions (Pannock and Didion, 1991). (a) Relative volumetric capacity. (b) Relative COP.
mass fraction should be about 50% for R32/R152a to have better cooling and heating
performance than R22. One interesting result of R32/R152a is that the heating COP
has two peak COPs as the R32 mass fraction increases. Pannock and Didion (1991)
explained this phenomenon by the temperature glide of the mixture: the first maxi-
mum is reached at the point of best glide matching and the COP decreases by the
further increase in R32 mass fraction due to the excessive temperature glide of the
mixture. However, the temperature glide of the mixture starts to decrease by further
increase of the R32 mass fractions, which results in the second peak in the COP by

80
Vol. Capacity Improvement over R22 [%]

60
R32/R134a
40
20
R32/R152a
0
−20
−40
−60
0 0.2 0.4 0.6 0.8 1.0
R32 Mass Fraction
(b)
10
R32/R152a
COP Improvement over R22 [%]
R32/R134a
5
−5
0 0.2 0.4 0.6 0.8 1.0
R32 Mass Fraction
(b)
FIGURE 3.10.4 Performance of R32/R152a and R32/R134a at ASHRAE Heating 47S con-
ditions (Pannock and Didion, 1991). (a) Relative volumetric capacity. (b) Relative COP.
better temperature glide matching. However both mixture components of R32/R152a

are flammable though it has the lowest GWP out of the 15 considered mixtures.
The volumetric capacity of R32/R152a reached that of R22 at 27 and 30% of
R32 mass fraction for cooling and heating, respectively. The maximum COP of
R32/R152a for cooling and heating was reached at about 50 to 70% of R32 mass
fraction. The R32 mass fraction should be about 50% for R32/R134a to have better
cooling and heating performance than R22, the same result with R32/R152a though
R32/R134a showed a better volumetric capacity but worse COP than those of

R32/R152a for the same R32 mass fraction. R134a is not flammable, so R32/R134a
is definitely less flammable than R32/R152a. Experimental results of these two
mixtures are referred to the same study explained in Section 5.1.2.
This investigation of binary zeotropic mixtures showed their potential as alter-
native refrigerants for R22. It was also found that matching the temperature glide
of the refrigerant and air are important to show zeotropic mixtures’ potential. In
actual residential air conditioners, the indoor heat exchanger can approach cross-
counter flow but the outdoor heat exchanger cannot since the number of rows is
typically one or two. The temperature glide of mixtures then is not utilized in the
outdoor heat exchanger. Another situation to be noted is the refrigerant flow reversal
case by changing operating mode from one to another. The temperature glide of
mixtures is then not utilized in the cross-counter flow type indoor coil during the
heating mode, as will be discussed in Section 5.2.
3.10.2.3 Refrigerant Performance Comparison
Domanski and Didion (1993) also reviewed the performance of nine R22 alternatives,
as listed in Table 3.6. The number in the first column of this table designates each
refrigerant in Figures 3.10.5 through 3.10.7. Using these nine refrigerants, three cycle
options were investigated: drop-in, system modification, and system with SLHX.
In this model analysis, the following assumptions were made:
• Overall compressor polytropic efficiency: 0.7
• Pure crossflow heat exchangers for both evaporator and condenser
• Zero degree of superheating at the evaporator outlet
• Zero degree of subcooling at the condenser outlet
• Fixed pressure drop across heat exchangers (both evaporator and con-
denser): 34.5 kPa
• Fixed heat transfer fluid inlet and outlet temperatures (Table 3.7)
TABLE 3.6
Refrigerants Investigated
Molecular Mass Tdew [˚C]
No. Refrigerant Mass Fraction [%] [kg/kmol] at 1 atm Tglide [˚C]
0 R22 100 86.5 –40.9 0

1 R32/125 60/40 67.3 –53.1 0
2 R32/125/134a/290 20/55/20/5 86.8 –45.2 8.5
3 R32/125/134a 10/70/20 102.9 –42.4 5.4
4 R290 100 44.1 –40.0 0
5 R32/125/134a 30/10/60 80.1 –36.0 7.6
6 R32/227ea 35/65 94.8 –35.3 20.6
7 R32/134a 30/70 79.2 –34.4 7.3
8 R32/134a 25/75 82.3 –33.1 7.0
9 R134a 100 102.0 –26.2 0
Source: Domanski and Didion, 1993.

0.8 0.2
35°C (95°F) 27.8°C (82°F)
35°C (95°F) 27.8°C (82°F) 8.3°C (47°F) −8.3°C (17°F)
0.6
8.3°C (47°F) −8.3°C (17°F)
0.1
(COP–COPR22)/COPR22
0.4
(Q–QR22)/QR22
0.2
0
0
−0.2
−0.1
−0.4
−0.6 −0.2
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
Refrigerant/Mixture Refrigerant/Mixture
(a) (b)
FIGURE 3.10.5 Drop-in performance (Domanski and Didion, 1993). (a) Relative volumetric capacity. (b) Relative COP.

0.8 0.2
35°C (95°F) 27.8°C (82°F) 35°C (95°F) 27.8°C (82°F)
0.6
8.3°C (47°F) −8.3°C (17°F) 8.3°C (47°F) −8.3°C (17°F)
0.1
(Qvol–Qvol,R22)/Qvol,R22
0.4
0.2
0
0
−0.2
−0.1
−0.4
−0.6 −0.2
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
(a) (b)
FIGURE 3.10.6 Performance of modified system (Domanski and Didion, 1993). (a) Relative volumetric capacity. (b) Relative COP.

0.8 0.2
35°C (95°F) −8.3°C (17°F) 35°C (95°F) −8.3°C (17°F)
0.6
0.1
(Qvol–Qvol,R22)/Qvol,R22
0.4
0.2
0
0
−0.2
−0.1
−0.4
−0.6 −0.2
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9
(a) (b)
FIGURE 3.10.7 Performance of system with SLHX (Domanski and Didion, 1993). (a) Relative capacity. (b) Relative COP.

TABLE 3.7
Heat Transfer Fluid (Air) Temperatures
Mode Cooling A Cooling B Heating 47S Heating 17L
Condenser Inlet 35.0˚C 27.8˚C 21.1˚C 21.1˚C

Condenser Outlet 43.2˚C 37.4˚C 32.5˚C 28.1˚C
Evaporator Inlet 46.7˚C 26.7˚C 8.3˚C –8.3˚C
Evaporator Outlet 14.4˚C 13.8˚C 2.7˚C –11.3˚C
Source: Domanski and Didion, 1993.
In the drop-in performance analysis, it was assumed that there was no system
modification except the expansion device. The compressor RPM, displacement vol-
ume and heat exchanger areas were fixed as those of the R22 system. Figure 3.10.5
shows drop-in performance results. The refrigerant that has the higher saturation
pressure has the higher volumetric capacity. R32/R125 has the highest volumetric
capacity and R134a has the lowest volumetric capacity. However, the COP results
were reversed: the refrigerant that has higher saturation pressure has the lower COP.
The second analysis was the performance comparison under equal heat
exchanger loading as suggested by McLinden and Radermacher (1987). In this
analysis, the overall heat capacities of evaporator and condenser (UAe and UAc) and
average evaporation temperature (Te,avg) were selected such that the R22 saturation
temperatures at the evaporator and condenser outlet were 7.8 and 46.1˚C, respec-
tively, at cooling A test condition. The system was then modified for each refrigerant
such that the two constraints of Equations 3.50 and 3.51 were satisfied. Equation
3.50 requires the same heat exchanger area loading and Equation 3.51 requires a
specific size of the evaporator.
Qe
= const as R22 value (3.50)
UAe + UAc
Te ,avg = const as R22 value (3.51)
Figure 3.10.6 shows the performance of the refrigerants in the modified system.
This figure shows that the modified system has a larger change in volumetric capacity
than the drop-in case since a larger heat exchanger area is required as the volumetric
capacity increases (Equation 3.50). This effect on the volumetric capacity minimized
the penalty in COP, so the modified system has less change in COP than the drop-
in case. One important result is that the COPs of all nine refrigerants are lower than
that of R22.
The third analysis was conducted for the modified system with a SLHX. This
analysis was done on cooling for ASHRAE A and the 17L heating conditions. It was
further assumed that the SLHX effectiveness was 45%. Figure 3.10.7 shows results
of an analysis for the system with SLHX. The COP of the modified system with the

SLHX improved over that without the SLHX. Most refrigerants except R32/R227ea
showed a comparable COP with R22 within 5%.
3.10.2.4 ORNL Model: BICYCLE and Mark V
Simplified Cycle Model: BICYCLE

Rice et al. (1993) developed a simplified model, BICYCLE, for modeling design
and evaluation of off-design performance of R22 alternative refrigerant mixtures in
a vapor compression cycle. In BICYCLE, the following assumptions were used.
• Effects of dehumidification on the heat exchanger UA values are included

based upon the sensible heat ratio results of R22.
• UA variation due to the changes in heat exchangers function from cooling
to heating mode: –25 to +20%.
• R22 baseline conditions at the compressor suction and discharge: saturated
temperatures of 8.9˚C/47.8˚C.
• Zero degree of superheating at the evaporator outlet.
• Zero degree of subcooling at the condenser outlet.
• A constant total UA value (HX loading) across both heat exchangers
(similar to Equation 3.50).
• Counterflow heat exchangers.
• Fixed pressure drops across the heat exchangers (both evaporator and
condenser): 34.5 kPa.
• Compressor volumetric efficiency was given as a function of pressure
ratio based on the compressor calorimeter tests.
• Compressor isentropic efficiency was given as a function of ambient
temperature but was the same for different refrigerants.
• Compressor shell heat loss was 10% of the compressor power input.
Based on the assumptions made above, BICYCLE simulates cycle performance

at specified airflow rates (or temperature change across the heat exchanger), heat
exchanger UAs and capacity. BICYCLE was verified by comparing its results with
results of the detailed model Mark IV and showed an agreement within 4% over a
range of cooling and heating conditions. Then the BICYCLE was applied to four
different refrigerant mixtures selected from the Alternative Refrigerants Evaluation
Program (AREP, 1993) to cover azeotropic mixtures and zeotropic mixtures having
small and large temperature glides. Those were one azeotropic mixture, R32/R125
(60/40 wt.%), two small temperature glide mixtures, R32/R134a (30/70 wt.%) and
R32/R125/R134a (30/10/60 wt.%), and one large temperature glide mixture,
R32/R227ea (35/65 wt.%). For these mixtures, BICYCLE was applied at the same
airflow rate, UA values and sensible heat ratios as for R22. Only the compressor
displacement was adjusted to obtain the same design capacity.
Results of the calculations are shown in Figure 3.10.8. As intended, all mixtures
have the same capacity as R22 at cooling test A conditions. In Figure 3.10.8(b), the
COP prediction by Rice et al. (1993) with counterflow heat exchangers are compared
to those by Domanski and Didion (1993) as shown by the horizontal lines for

(a)
ORNL-DWG 83-1887A
10
8 Same
6 Design Capacity
% Capacity Difference Relative to R-22
(Same Nominal Design Capacity)
4
2
0 R-22
−2
−4
R-32/R-125 [60/40]
−6
−8 R-32/R-134a [30/70]
−10
R-32/R-125/R-134a [30/10/60]
−12
−14 R-32/R-227ea [35/65]
−16
−18 Heating Cooling
−20
Low-Temp High-Temp Low-Temp High-Temp
Heat Pump Ambient Conditions
(b)
ORNL-DWG 83-1886A
10
8 R-32/R-125 [60/40] R-32/R-125/R-134a [30/10/60]
6 R-32/R-134a [30/70] R-32/R-227ea [35/65]
% COP Difference Relative to R-22
4
2
0 R-22
−2
−4
−6
−8
−10
−12
−14
−16 Domanski and
−18 Heating Didion (1993) Cooling
−20
Low-Temp High-Temp Low-Temp High-Temp
Heat Pump Ambient Conditions
FIGURE 3.10.8 Performance of four refrigerant mixtures (Rice et al., 1993). (a) Relative
capacity and COP. (b) Relative heating seasonal performance factor (HSPF).
crossflow heat exchangers with more restrictive conditions (Equation 3.51). As

shown in Figure 3.10.8, R32/R125 showed a higher heating capacity especially at
the 17L conditions but 4 to 5% lower COP for all test conditions. Two small
temperature glide mixtures, R32/R134a and R32/R125/R134a, showed a 2 to 5%

lower heating capacity but 4 to 5% higher COP for all tests conditions. R32/R227ea
is the only one that showed lower heating capacity and COPs for more test conditions
than those of R22. This degradation is because of the excessive refrigerant temper-
ature glide resulted in a heat exchanger temperature pinch that forced the mean
refrigerant temperature down in the evaporator and up in the condenser.
As shown in Figure 3.10.8 the low temperature heating capacity of the low
temperature glide mixtures is 4 to 6% lower than that of R32/R125. To investigate
the potential for improvement of the low heating performance of the small temper-
ature glide mixtures, passive and active composition shifting was examined for these
mixtures. The utilization of the suction line accumulator enables passive control
over the composition shift by varying the amount of the liquid refrigerant depending
on the ambient temperature. For the passive control, it was assumed that the mass
fraction of R32/R134a was 36/64 wt.%, based on Shiflett’s (1993) results, and the
mass fraction of R32/R125/R134a was 36/12/52 wt.%. A cycle with rectifier offers
active composition shift control. For the active control, it was assumed that the mass
fraction of R32/R134a was 48/52 wt.% and the mass fraction of R32/R125/R134a
was 48/16/36 wt.%. Details of capacity control by the composition shift are discussed
in Chapter 7. The results of passive and active composition shift are shown in Figure
3.10.9. The results showed that R32/R134a gained 5 and 16% heating capacity over
its original composition for the passive and active composition shift, respectively.
For the R32/R125/R134a, the capacity gains were 7 and 19%, respectively. However,
the COP of R32/R134a was reduced by 2 and 5% for the passive and active
composition shift, respectively. For the R32/R125/R134a, the COP loss was 7 and
19%, respectively. Figure 3.10.9(b) shows the heating seasonal performance factor
(HSPF) of three mixtures with the composition shift options for the climate region
IV and V. R32/R125 showed about 2% higher HSPF than that of R22. R32/R134a
and R32/R125/R134a also showed 2% better HSPF for the passive composition shift
and 5 to 8% better HSPF for the active composition shift than that of R22. The
predicted cooling seasonal energy efficiency ratio (SEER) of RR32/R125 was about
4% less than that of R22 while those of R32/R134a and R32/R125/R134a was 5 to
6% higher than R22.
Design Cycle Model: Mark V
Oak Ridge National Laboratory (ORNL) has developed and distributed a series of
versions of DOE/ORNL Heat Pump Design Model (HPDM) that is a hardware-based,
steady-state performance simulation model since 1978 as summarized by Rice (1997).
Ellison and Creswick (1978) developed the first ORNL version of a cycle model
based on an MIT model developed by Hiller and Glicksman (1976). Fisher and Rice
(1983) then released the first major revision called Mark I. Fisher et al. (1988) released
Mark III as a PC DOS version. In 1991, Spatz reported using a modified version of
the Mark III model to first identify the system potential of R410A, considering
transport and thermodynamic property effects on heat exchanger performance. Rice
(1987 and 1988) added charge inventory capability and Rice (1991) completed a
variable-speed model of the Mark III by adding electronically commutated motors
and design parametric capability, called Mark IV. Recently, ORNL released the Mark
V version (1994). The latest version of this model includes the variable-speed

(a)
ORNL-DWG 83 -1864
20
COP Low-Temp Heating
15 Capacity
10
5
relative to R-22
% Difference
0 R-22
−5
O O P A O P A
−10
O = Original Composition
−15 P = Passive Composition Shift (6% Wt. Shift R-32)
A = Active Composition Shift (18% Wt. Shift R-32)
−20
R-32/R-125 R-32/R-134a R-32/125/134a
[60/40] [30/70] [30/10/60]
R-22 Alternatives
(b)
ORNL-DWG 83 -1863
10
DOE Region IV
8
DOE Region V
6 (Maximum DHR)
4
relative to R-22
2
% Difference
0 R-22
−2 O O P A O P A
−4
−6 O = Original Composition
P = Passive Composition Shift (6% Wt. Shift R-32)
−8 A = Active Composition Shift (18% Wt. Shift R-32)
O
−10
R-32/R-125 R-32/R-134a R-32/125/134a R-32/R-227ea
[60/40] [30/70] [30/10/60] [35/85]
R-22 Alternatives
FIGURE 3.10.9 Performance of four refrigerant mixtures with composition shift (Rice et al.,
1993a).

compressor model, properties of R410A, R407C, R404A (near-azeotropic HFC alter-

natives to R22) and propane (natural refrigerant).
3.10.2.5 University of Maryland Model: HAC1 and HPCYCLE
Simplified Cycle Model: HAC1

Jung and Radermacher (1989) developed a UA-model, HAC1, to analyze the per-
formance of working fluids theoretically. In this model, the same heat exchanger
loading was applied for all refrigerants, which meant the air-side temperature dif-
ference and air flow rate were kept constant for the evaporator independent of the
types of refrigerants as proposed by McLinden and Radermacher (1987). In the
HAC1, the following assumptions were used.
• Zero degree of superheating at the evaporator outlet.

• Zero degree of subcooling at the condenser outlet.
• A constant UA value for each heat exchanger: U 0.1 kW/m2-K (17.6 Btu/ft2-
h˚F), Aev 4.0 m2 (43 ft2), Aco 5.0 m2 (54 ft2).
• Counterflow heat exchangers.
• Zero pressure drops across heat exchangers (both evaporator and condenser).
• Compressor isentropic efficiency: 0.7.
• Air flow rate: 0.19 m3/s (400 cfm) for indoor side, 0.38 m3/s (800 cfm)
for outdoor side.
• Fixed air temperatures for cooling mode: indoor unit air inlet and outlet
temperatures (26.7˚C, 11.1˚C) and outdoor unit air inlet temperature
(35.0/27.8˚C).
• Fixed air temperatures for heating mode: indoor unit air inlet temperature
(21.1˚C) and outdoor unit air inlet and outlet temperatures (8.3˚C,
0.6/–8.3˚C).
• Only a sensible cooling load was considered.
Table 3.8 shows the list of refrigerants investigated as R22 alternatives. It should be
noted that the constituents of the binary mixtures were selected such that one of low
boiling point refrigerants (R143a, R32 and R125) and one of high boiling point
refrigerants (R152a, R134, R134a and R124) were mixed to minimize the operating
pressure deviation from that of R22. The refrigerant components of the ternary
mixtures were selected such that R32 and R152a were mixed with nonflammable
refrigerants (R134, R134a and R124) to reduce the overall flammability. The mass
fraction of each component was determined to maximize the cooling COP at 35˚C
outdoor conditions. The maximum COP of R143a/R134a and R125/R134a were
obtained when the mass fraction of R134a was zero. These two binary mixtures
were eliminated from the further analysis.
Table 3.9 shows the performance comparison of pure refrigerants tested at 35˚C
outdoor conditions. Results indicated that R32 would help to increase the volumetric
capacity whereas R124, R134 and R134a would decrease the volumetric capacity.
R152a and R134 would help to increase COP, whereas the others would diminish
the COP.

TABLE 3.8
List of Refrigerants Investigated
Pure Refrigerant Binary Refrigerant Ternary Refrigerant
R32 R32/R134a (30/70 wt.%) R32/R152a/R134a (40/50/10 wt.%)

R124 R32/R152a (40/60 wt.%) R32/R152a/R134 (30/40/30 wt.%)
R125 R32/R134 (30/70 wt.%) R32/R152a/R124 (20/20/60 wt.%)
R134 R32/R124 (30/70 wt.%)
R134a R143a/R134a (100/0 wt.%)
R143a R143a/R152a (10/90 wt.%)
R152a R143a/R124 (30/70 wt.%)
R125/R134a (100/0 wt.%)
R125/R152a (20/80 wt.%)
R125/R124 (50/50 wt.%)
Source: Radermacher and Jung, 1993.
TABLE 3.9
Performance Comparison of Pure Refrigerants Investigated
Pure Refrigerant COP COP Changes [%] Volumetric Capacity [kJ/m3]
R22 3.37 0 3735

R32 3.23 –4.2 6227
R124 3.04 –9.8 1382
R125 2.45 –27.4 3305
R134 3.44 2.0 1940
R134a 3.33 –1.2 2342
R143a 2.89 –14.3 3441
R152a 3.56 5.8 2308
Source: Radermacher and Jung, 1993.
The performance of the binary and ternary mixtures is compared in Figure

3.10.10. As shown, four refrigerants (R32, R32/R152a, R32/R134a and
R32/R152a/R134a) showed higher volumetric capacity than that of R22 and twelve
refrigerants showed higher COP than that of R22. The COP of R32/R152a/R124
was the highest and 14% higher but had 23% lower volumetric capacity than those
of R22. R32/R124 was the best binary mixture having 13% higher COP but 10%
lower volumetric capacity than those of R22. R32/R152a showed 13% COP and 2%
volumetric capacity improvement over R22.
Since R32 mixtures certainly showed better COP than that of R22, only R32
mixtures were further investigated for their seasonal performance factors (SPFs) for
both cooling and heating (CSPF and HSPF). It should be noted that only R22 and
R32 binary mixtures were examined. CSPF and HSPF were evaluated based on
ASHRAE Temperature Bin Method for the unitary air conditioners and heat pumps,

COP
4 (2878) (3377) (3439) (3809) (3512) (3865)
(2511) (3820) (2170) (2413) (2308) (VCR kJ/m3)∗
(3735) (1940)
(2342)
(6227)
(1382)
(3441)
3
(3305)
0
R-22 R-32/ R-32/ R-32/ R-32/ R-143a/ R-134 R-32 R-143a
R-124 R-152a R-152a/ R-134a R-152
R-134a
R-32/ R-32/ R-32/ R-125/ R-143a/ R-152a/ R-134a R-124 R-152
R-152a/ R-152a/ R-134 R-152a R-124
R-124 R-134
∗Numbers in parentheses represent the volumetric capacity (VCR kJ/m3) for each refrigerant
FIGURE 3.10.10 Performance comparison at 35˚C outdoor temperature (Radermacher and

Jung, 1993).
ASHRAE Standard 116 (1995). The HSPF was evaluated for six climate regions.
Results of SPFs are shown in Figure 3.10.11. As shown, R32/R152a exhibited the
best SPFs, followed by R32/R134 and R32/R134a.
In order to examine the potential capacity control capability through the con-
centration shift, it was assumed that the active concentration control could achieve
a 20% shift. Then the SPF was evaluated for R32/R152a and R32/R124. As shown
in Figure 3.10.12, CSPF was not affected by the concentration shift but the HSPF
was increased by 10% for R32/R124 and 6% for R32/R152a.
Detailed Transient Cycle Model: HPCYCLE
Judge (1996) developed a fully implicit, distributed parameter simulation, HPCYCLE,
capable of modeling the transient and steady state aspects of an air conditioner and
heat pump. For the steady state, the simulation solved the complete continuity,
species, energy and momentum equations while transiently only the momentum
equation was omitted. The cycle simulation consisted of cycle component simula-
tions. The simulation was applied for both R22 and R32/R134a (30/70 wt.%) to
study several different system configurations transiently and at steady state.
From the experimental results, it was found that there was essentially no perfor-
mance difference between R22 and R32/R134a. In addition, most of the R32/R134a
quantities except the refrigerant temperature and the refrigerant concentration were
almost identical to R22. Therefore, these two aspects will be explained further.
SPF
6
0
CSPF HSPF I HSPF II HSPF III HSPF IV HSPF V HSPF VI
R-22 R-32/R-152A R-32/R-134 R-32/R-134a R-32/R-124
FIGURE 3.10.11 Seasonal performance factor (SPF) comparison (Radermacher and Jung,
1993).
SPF
6
0
CSPF HSPF I HSPF II HSPF III HSPF IV HSPF V HSPF VI
R-32/R-152a R-32/R-152a w/Shift R-32/R-124 R-32/R-124 w/Shift
FIGURE 3.10.12 Effects of concentration shift on seasonal performance factor (Raderma-

cher and Jung, 1993).
Figure 3.10.13 shows the refrigerant temperature of R22 and R32/R134a at the
inlet of the four-cycle components over time. Two different aspects of the refrigerant
temperature of R32/R134a as compared to R22 are as follows: The temperature
entering the evaporator closely reproduces the trends of the low side pressure since
380
360 Condenser
Temperature (K)
340
320 STR
300
Compressor
280
260 Evaporator
240
0 60 120 180
Time (seconds)
(a) R22
380
360
Condenser
340
Temperature (K)
320
STR
300
Compressor
280
260 Evaporator
240
0 60 120 180
Time (seconds)
(b) R32/R134a
FIGURE 3.10.13 Refrigerant temperature entering each component (Judge, 1996).
it is in the two-phase region. The temperature leaving the evaporator follows the
inlet temperature of the evaporator until the exiting refrigerant becomes superheated
vapor. The temperature of the refrigerant leaving the compressor abruptly increases
after it has leveled off. This occurs because in the beginning there is liquid refrigerant
in the compressor shell that supplies the compressor with saturated vapor. The abrupt
increase occurs when there is no longer any liquid in the compressor shell and, as
a result, the compressor receives superheated vapor. The temperature of the refrig-
erant leaving the condenser and entering the expansion device changes little when
compared to the other temperatures. This is primarily due to the large heat transfer
area of the condenser that allows the outlet refrigerant temperature to closely
approach the outdoor temperature that remains constant. Although very similar to
the plot for R22 there are a few points that make it unique. The most notable
difference is at the compressor inlet. The temperature at the compressor inlet does
not follow the temperature of the evaporator inlet, as did R22 in the early transients.
This is a result of the temperature glide that occurs during the phase change of a
zeotropic mixture. Another difference is the considerably lower condenser inlet
temperature. This is a consequence of the higher specific heat of R32/R134a. Also
noteworthy is the slightly lower evaporator inlet temperature of R32/134a as com-
pared to R22.
The refrigerant concentration is the other quantity that makes R32/R134a unique
from R22. Figure 3.10.14 shows the R32 concentration of R32/R134a versus time
0.5
0.4
R-32 Concentration (kg/kg)
Circulated Concentration
0.3
Charged Concentration
0.2
0.1
Compressor Condenser STR Evaporator
0
0 60 120 180
Time (seconds)
FIGURE 3.10.14 R32 concentration entering each component (Judge, 1996).
at six different locations. Some important aspects of the R32 concentration changes
of R32/R134a are listed below.
Initially, the refrigerant leaving the evaporator and entering the compressor is
depleted of the more volatile component, R32. This is because at start-up, the
refrigerant in the evaporator is in the two-phase region and contains less R32 than
the charged concentration. On the other hand, the vapor, initially in equilibrium with
the refrigerant in the evaporator, is rich in R32 and occupies the condenser. Hence,
the condenser acts like a reservoir of R32 and the evaporator acts like a reservoir
of R134a. As time proceeds, the two-phase, R134a-rich, refrigerant enters the com-
pressor. There the compressor shell separates the liquid from the vapor so that the
compressor compresses only R32-rich vapor. As a consequence the refrigerant leav-
ing the compressor is still relatively rich in R32. However, as the liquid leaves the
evaporator and the amount of liquid in the compressor shell decreases, the R32
concentration leaving the compressor starts to decline. This subsequently causes the
decline in the R32 concentration leaving the condenser. These processes continue
until the circulated concentration is reached at the inlet to each component.
REFERENCES
Aaron, D.A. and P.A. Domanski, 1990, “Experimentation, analysis, and correlation of refrig-
erant 22 flow through short-tube restrictors,” ASHRAE Transactions, Vol. 96, Pt. 1,
pp. 729–742.
Air-Conditioning and Refrigeration Institute, 1997, “Positive Displacement Refrigerant Com-
pressors,” Compressor Units and Condensing Units, ARI Standard 520.
Air-Conditioning and Refrigeration Institute, 1999, “Method for Presentation of Compressor
Performance Data,” ARI Standard 540.
Air-Conditioning and Refrigeration Institute, 1993, “Results from ARI’s R22 Alternative
Refrigerants Evaluation Program (AREP),” Compressor Calorimeter, System Drop-
in, Soft Optimized System Test Reports, Vol. 4, Report #157.
Alefeld, G., 1987, “Efficiency of Compressor Heat Pumps and Refrigerators derived from the
Second Law of Thermodynamics,” International Journal of Refrigeration, Vol. 10,
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4 Methods for Improving
the Cycle Efficiency
Several options for the incremental efficiency improvement of the vapor compression
cycle are available. In addition, based especially on the understanding of the refrig-
erant properties and how they affect cycle performance, very significant additional
improvements are available when the cycle is modified and new components are
added. Three measures are discussed in this chapter, the suction line to liquid line
heat exchanger, the economizer and the isentropic expansion device. While these
devices also benefit cycles with pure fluids, they have unique effects for mixtures
when considered in conjunction with the temperature glide. For mixtures alone, one
additional option exists — the three-path evaporator.
4.1 MEASURES OF INCREMENTAL

EFFICIENCY IMPROVEMENT
One obvious concern in vapor compression systems is the pressure loss in the
connecting piping. Significant efficiency improvements are possible when the pres-
sure drop is minimized. Pipe diameters must be selected so that the pressure drop
is small, even though larger pipes contribute to an increased first cost. In addition,
especially in the suction pipe, the vapor velocity must be sufficiently high to ensure
proper oil return to the compressor. The pressure drop within the heat exchangers
should also be minimized. But here again a trade-off exists: Low pressure drop
means large tube diameters and low fluid velocities. These in turn lead to poor heat
transfer coefficients. Lastly, the flow channels within the compressor and especially
the suction and discharge valves (if used in a given compressor type) can contribute
significantly to pressure drop and greatly influence overall compressor performance.
While a reduction in pressure drop is very desirable, there can be a number of
competing effects that limit the level of reduction.
Another measure to improve cycle performance is avoiding evaporator superheat.
When the evaporator outlet is saturated vapor, the entire evaporator surface area is
used for the purpose of evaporating refrigerant. This occurs at the lowest temperature
in the system and at very good heat transfer coefficients. However, some superheat
is required to ensure that the compressor is not exposed to any liquid that can be
entrained in the suction vapor. The vapor is superheated within the evaporator using
valuable surface area. The superheating process absorbs much less heat for a given
evaporator area than evaporation because the specific heat capacity is low for super-
heating, the heat transfer coefficient is low and the average temperature difference is
smaller than for evaporation. When superheating is required, the evaporator saturation
135
d Water
Chille
t
hea
Evaporation without
per
Superheat
Su
Evaporation with
Superheat
Heat Exchanger Length
FIGURE 4.1.1 The need for superheat can lower the evaporation temperature.
ln (P)
Chilled Water Refrigerant

without
Superheat
Reduction
in Suction
Pressure Refrigerant with
Superheat
FIGURE 4.1.2 The need for superheat can require a lower suction pressure and thus lower
compressor capacity.
temperature is pushed to a somewhat lower level. This is described in Figures 4.1.1

and 4.1.2 for water chilling.
It should be noted that superheating also increases compressor work per unit
mass of refrigerant (explained in more detail in the following chapter) and reduces
the compressor volumetric capacity. Since the vapor density is also lower, the
compressor pumps a smaller refrigerant mass flow rate. This reduces the cooling
capacity of the system.
For refrigerant mixtures, a temperature glide exists and the penalty for super-
heating remains essentially the same. The influence of the reduced temperature
difference can be aggravated by the glide. The argument of the reduced heat transfer
coefficient for superheating still applies.
A similar but somewhat more complex situation exists at the condenser outlet.
Any subcooling reduces the condenser heat transfer area that is available for con-
densation and increases the condenser saturation temperature. Alternatively, sub-
cooling benefits the evaporator capacity by reducing the enthalpy at the inlet to the
evaporator. The designer must find a trade-off between these two competing effects.
Methods for Improving the Cycle Efficiency 137
ln (P)
4a 4
T5
5a
T5a
FIGURE 4.1.3 Effects of subcooling.
ln (P)
4a 4
TB 2 TA
5a
TB
FIGURE 4.1.4 Effects of subcooling for two refrigerant mixtures having different isotherms.
When zeotropic mixtures are used, the subcooling has two effects on the evap-
orator inlet conditions. As with pure fluids, subcooling reduces the enthalpy and
increases the capacity of the evaporating fluid. At the same time, as a result of the
glide, the inlet temperature to the evaporator is reduced, as shown in Figure 4.1.3.
With increased subcooling from 4 to 4a, the evaporator inlet state point changes
from 5 to 5a. As can be seen in Figure 4.1.3, the temperature T5a is lower than T5.
However, depending on the slope of the two-phase isotherm in this portion of the
two-phase region, the decreased inlet temperature effect can be more or less pro-
nounced. Figure 4.1.4 shows examples of isotherms for two different refrigerant
mixtures, A and B. The isotherm TA of refrigerant mixture A has an almost horizontal
slope in the low quality region close to the saturated liquid line. TB and TB2 of mixture
B have a relatively steep slope. Thus, the effect of subcooling on reducing the
evaporator inlet temperature as shown in Figure 4.1.3 is much less pronounced for
a mixture that exhibits an isotherm of type TA. There is essentially no difference in
temperature between points 5a and 5. For an isotherm of type TB, however, point 5a
is located on the lower temperature isotherm TB while point 5 lies on TB2, TB < TB2.
This reduction of the evaporator inlet temperature has interesting consequences.
The suction pressure can be increased slightly in order to maintain a constant
evaporator capacity as long as the glide is still well matched. The compressor power
consumption is reduced. This proposal assumes that an increase in subcooling does

not push up the condenser pressure to the degree that it overcompensates for the
benefit in the evaporator. If the subcooling enhances a glide mismatch, the perfor-
mance will degrade.
4.2 THE SUCTION LINE TO LIQUID LINE

HEAT EXCHANGER
The following consideration focuses first on pure refrigerants. Figure 4.2.1(a) shows
a schematic of a vapor compression cycle with a suction to liquid line heat exchanger
and Figure 4.2.1(b) the corresponding ln(P)-h diagram. The purpose of the heat
exchanger is to increase the evaporator capacity. When saturated liquid leaves the
condenser at point 4, the evaporator capacity is determined by the enthalpy difference
h1 – h5 as shown in Figure 4.2.1(a). The further the liquid condensate can be
subcooled, the lower the enthalpy of that liquid becomes (4a) and, therefore, the
enthalpy at the inlet of the evaporator (5a). Thus, a high degree of subcooling is
very desirable from this point of view. However, the temperature T4a is lower than
the temperature T4, as seen in Figure 4.2.1(b). Subcooling requires that a heat sink
is available at sufficiently low temperatures.
One heat sink is always lower than any external heat sink — the suction vapor.
The suction vapor can be used to subcool the liquid condensate as indicated in Figure
4.2.1(a). The arrow in Figure 4.2.1(b) indicates the transfer of heat, i.e., the enthalpy
4 Condenser 2
3 Compressor
1a (a)
4a Suction Line to
Expansion Liquid Line Heat
Valve Exchanger
Evaporator
5, 5a 1
ln (P)
T4a T4
4a 4 3 2
(b)
5a 5 1 1a
h 5a h1 h
FIGURE 4.2.1 (a) Schematic of vapor compression cycle with suction line to liquid line heat
exchanger. (b) The state points according to (a) on an ln(P)-h diagram. The arrow indicates
the direction of heat transfer.
difference h4 to h4a from the subcooled liquid to the suction gas (h1a – h1). Thus, the
suction gas is superheated and its enthalpy increased by
qslhx = h4 − h4 a = h1a − h1 (4.1)
while the inlet enthalpy to the evaporator is lowered by the same qslhx. This transfer
of heat enables one to transfer cooling capacity de facto from the evaporator satu-
ration temperature level via the suction heat exchange to the temperature level of
the (warmer) suction gas as it is being superheated.
This benefit comes with a challenge. The suction gas is superheated and the
state point for the superheated gas moves into a region of the ln(P)-h diagram where
the isentropes become flatter and the compressor work input increases. Thus, the
benefit of the suction to liquid line heat exchanger depends strongly on whether or
not the benefit outweighs the penalty of increased compressor work. This strongly
depends on the working fluid used.
As a rule, the following consideration applies: The higher the specific heat
capacity of the refrigerant molecules, the higher the benefit of the suction to liquid
line heat exchange. A high specific heat capacity of the refrigerant has two effects:
The temperature increase during the compression process is low, the compressor
compresses a gas that heats up less and the compressor work does not increase as
much because of the lack of superheat. However, during the expansion process a
relatively large amount of refrigerant must evaporate to cool the remaining liquid
to the evaporator saturation temperature.
This situation is better understood when the ln(P)-h diagram for a refrigerant of
high specific heat capacity is compared to a refrigerant of low specific heat. Figure
4.2.2 shows two diagrams side by side; (a) shows the diagram of a low capacity
refrigerant, (b) that of a high heat capacity fluid. Obviously, the vapor dome is much
tilted more to higher enthalpies for the high heat capacity fluid as shown in Figure
4.2.2(b). As a consequence, the expansion process produces much more vapor and
ln (P) ln (P)
h h
(a) (b)
FIGURE 4.2.2 (a) ln(P)-h diagram for a refrigerant of low specific heat capacity. (b) ln(P)-
h diagram for a refrigerant of large specific heat capacity.
less liquid. The evaporator capacity is reduced considerably. Furthermore, the com-
pression process stays very close to the saturated vapor line and the compressed
refrigerant vapor is almost not superheated at all. In fact, for some refrigerants, the
state point of the compressed vapor can be located in the two-phase range. In this
case, the penalty in terms of increased compressor work is small or even desirable
to avoid a two-phase condition at the compressor outlet. The benefit of improved
evaporator capacity is very important because otherwise the refrigerant would not
be very efficient.
For refrigerants of low specific heat capacity, the suction to liquid line heat
exchanger can have the opposite effect. Examples for fluids of low specific heat
capacity are ammonia, R22, R32 and other fluids with a small number of atoms in
the molecule. Refrigerants of high specific heat capacity are R123, R134a and other
such molecules with a large number of atoms within the molecule. When the number
of atoms is small, any addition of energy can only be transferred into translational
movement, increasing the temperature. When the number of atoms in a molecule is
large, additional energy is first transferred into internal degrees of freedom, such as
oscillations and rotations of the atoms within the molecule, and very little energy
into the translational movement. The resulting increase in temperature is small.
Figure 4.2.3 shows a plot of COP improvement when a suction to liquid line
heat exchanger is used with three levels of heat exchange efficiency, ηhx = 0.0
(baseline), ηhx = 0.5 and ηhx = 1.0. All COP values refer to the Carnot COP and all
values are evaluated at the same reduced temperature. The refrigerants on the x-axis
are sorted according to their vapor specific heat capacity beginning with the lowest
specific heat capacity. For low heat capacity fluids, the suction to liquid line heat
exchanger has an obvious detrimental effect. This is followed by a range where there
is no particular benefit and the higher specific heat capacity of the refrigerant
becomes more pronounced in the improvement resulting from the heat exchanger.
It should be noted that the fluids with a high specific heat capacity reach higher
fractions of the Carnot COP. From this point of view, refrigerants with high molecular
weights should be preferred. The trade-off is that the vapor pressure tends to be
very low for these fluids and system size increases considerably. Thus, the low
pressure refrigerants are best suited for large capacity machines.
For zeotropic mixtures, the suction to liquid line heat exchanger has an additional
effect as shown in the ln(P)-h diagram of Figure 4.2.4. By reducing the enthalpy at
the evaporator inlet, the temperature of the entering mixture is reduced because of
the influence of the glide. T5a is lower than T5, assuming that the suction pressure
level did not change because of the heat exchanger. This decrease in temperature at
the evaporator inlet increases the evaporator capacity because the temperature dif-
ference that drives the heat transfer is increased.
Alternatively, the suction pressure can be increased slightly and the penalty of
increased compressor work somewhat reduced. Depending on the size of the glide
and its linearity, this effect can be significant (steep glide close to the liquid line)
or nonexistent (flat glide close to the liquid line). See Figures 4.1.3 and 4.1.4 with
examples in Chapter 5 where experimental results are discussed.
COPhx/COPC
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
R-744
NH3
R-32
R-14
R-23
ηhor = 0.0
R-C270
R-22

R-13
ηnk = 0.5
R-13B1
R-152a
R-21
ηhx = 1.0
R-290
R-143a
R-12
R-143
R-134a
R-142b
R-125
R-11
R-134
R-600a
R-124
R-141b
E-134
R-115
R-600
R-123
FIGURE 4.2.3 Plot of COP improvement using suction to liquid line heat exchanger (Domanski, 1995).
R-123a
R-245cb
R-114
R-236ea
R-227ea
I-C5
R-113
N-C5
R-218
E-245
R-C31B
ln (P)
4a 4 3
2
Transfer
of Heat
5a 5 1 1a
T5a T5 T1
FIGURE 4.2.4 For zeotropic mixtures, the suction to liquid line heat exchanger lowers the
evaporator inlet temperature from T5 to T5a.
4.3 THE ECONOMIZER

The suction line to liquid line heat exchanger described above is a means to increase
the evaporator capacity by reducing the inlet enthalpy. The economizer aims at
reducing the compressor power. For example, upon inspection of the ln(P)-h dia-
gram, Figure 3.7.3, it is seen that the compressor must compress vapor generated
for cooling the remaining liquid refrigerant. This vapor does not contribute to the
cooling capacity of the evaporator but is generated across the entire temperature
range over which the refrigerant is cooled during the expansion process.
The economizer cycle extracts a portion of this vapor at an intermediate pressure
level and sends it to the compressor so that this portion of vapor is compressed from
that pressure level and higher. This process avoids the expansion of this vapor portion
to the evaporator pressure level, which represents a loss of avoidable work. Figure
4.3.1 shows an economizer cycle. The liquid condensate, state point 3, is expanded
in a first expansion valve and in the subsequent flash tank, liquid and vapor are
separated. The vapor is saturated; its state point is 7 and the state point of the
saturated liquid is 5. The vapor 7 is directed into a second compressor suction port
where it is mixed with partially compressed suction vapor and further compressed.
The liquid 5 is further expanded to the evaporator pressure level, point 6, and
evaporated as usual.
Figure 4.3.1 shows what appears to be an obvious increase in evaporator capacity.
State point 6 is shifted much further toward lower evaporator inlet enthalpies than
at point 6a, resulting from the expansion of the saturated liquid at 3. The mass flow
rate entering the evaporator is lower in the economizer cycle. The total amount of
liquid entering the evaporator is the same in both cases (except for a small effect)
as shown next.
The evaporator capacity for the case of the conventional cycle can be calculated
as
Q evap = m 3 (h1 − h3 ) (4.2)

3
Condenser
Expansion 2
Valve 1 4 7 Compressor
(a)
Expansion 5
Valve 2 1
Evaporator
6
ln (P)
3 2
5 4 78 9 (b)
6 6a 1
FIGURE 4.3.1 (a) State points superimposed on a ln(P)-h diagram. (b) Schematic of a vapor
compression cycle with economizer.
and for the economizer cycle as
Q evap,Eco = m 3 (1 − x 4 )( h1 − h5 ) (4.3)
where x4 is the fraction of the total mass flow rate that is extracted on the intermediate
pressure level.
The difference in evaporator capacity can be calculated as
∆Q = Q evap,Eco − Q evap (4.4)
When we calculate ∆Q , the following expression is obtained:
∆Q = m 3 [(1 − x 4 )( h1 − h5 ) − ( h1 − h3 )] (4.5)
where
x4 is the vapor quality at point 4
x4 can be expressed in terms of enthalpy as Equation 4.6
x4 = (h3 − h5 ) / (h7 − h5 ) (4.6)
After using Equation 4.6 for x4, the following final expression Equation 4.7 is
obtained:
h − h1
∆Q = m 3 (h3 − h5 ) 7 (4.7)
h7 − h5
Mass Fraction
T at Condenser
Exit
54 7
6
1
0 1.0
X
FIGURE 4.3.2 State points according to Figure 4.3.1 on T-x diagram.
Thus, the change in evaporator capacity because of the economizer feature is

shown to be proportional to the reduction in evaporator inlet enthalpy (h3 – h5) times
a correction term that is based on the difference in vapor enthalpies of the flash tank
exit (h7) and the evaporator outlet (h1). If this difference is zero, there is no benefit
in the evaporator capacity derived from the economizer cycle as expected. This
means both enthalpies are the same and therefore the saturated vapor line in the
ln(P)-h diagram is vertical in this region. Depending on whether h7 is larger or
smaller than h1, the change in ∆Q can be positive or negative, respectively.
While the economizer cycle might or might not be of benefit to the evaporator
capacity, it certainly has a benefit in terms of reduced compressor work for two
reasons. First, the compressor work in the lower compression stage is reduced
because the mass flow rate in the compressor is reduced to the amount of (1 – x4).
Second, as can be seen on the ln(P)-h diagram of Figure 4.3.1, the second stage of
the compression process operates with a lower suction temperature than would be
the case without the economizer.
When zeotropic refrigerant mixtures are used, the impact of the economizer
cycle is more complex. The vapor leaving the flash tank contains predominantly the
lower boiling component, while the liquid contains the higher boiling component.
This is shown in the T-x diagram of Figure 4.3.2 with the state points the same as
in Figure 4.3.1. Because of the separation in the flash tank, the mass fraction in the
evaporator is lower. For the same evaporation pressure, the coldest temperature in
the evaporator is now raised because of the composition shift. This effect is opposite
the one described above for suction heat exchangers.
It should be noted that because of the composition shift, the economizer cycle
cannot be correctly displayed on the ln(P)-h diagram for a mixture. These diagrams
are only valid for a given mass fraction and any change in mass fraction cannot be
meaningfully displayed. This would require a switch to the enthalpy-mass fraction
diagram. However, this diagram is not suitable for showing the superheated vapor
region and therefore the compression process cannot be shown.
3
4 Condenser 2
Power Compressor
Power Input
5a Evaporator
1
ope
ln (P)
Isentr
3 2
4
5a
5 1
∆W = ∆Qevap h
FIGURE 4.4.1 Vapor compression cycle with expander to recover expansion work.
To conduct performance calculations for a zeotropic mixture cycle with an

economizer using just one ln(P)-h diagram will lead to evaporator pressures that are
slightly too high and enthalpy values that are not quite correct. The larger the
difference in the boiling points of the two mixture constituents becomes, the higher
the actual value of these deviations.
4.4 THE EXPANDER

The expansion process reduces the pressure of the refrigerant from the condenser
level to the evaporator level in a process of constant enthalpy and is highly irrevers-
ible. As an alternative, a work-producing expansion device can be employed instead.
The power output of this device can then be supplied to the compressor to reduce
compressor power input. Figure 4.4.1 shows a schematic of this case. State point 5
represents the outlet condition after the conventional expansion process and state
point 5a represents the post-isentropic expansion process. In case of the isentropic
expansion, there is less refrigerant vapor produced in order to cool the fluid to the
evaporator temperature level because a portion of the energy content is removed in
the form of work. However, the saturation line is usually not reached. The isentropes
in the two-phase region are steeper than the saturated liquid line in a ln(P)-h diagram.
An inspection of Figure 4.4.1 reveals that the expander produces a double benefit.
As mentioned above, it produces work that reduces the power requirement of the
compressor. The amount of work produced by the expander can be calculated as
∆W = m ( h5 − h5 a ) (4.8)
This same amount of energy, since it is extracted from the refrigerant stream, also
represents an increase of evaporator cooling capacity as shown in Figure 4.4.1. The
new evaporator capacity is now calculated as
Q evap = m (h1 − h5a ) (4.9)
This benefit is available even when the work produced by the expander is not utilized.
However, to maximize the benefit of an expander, both the increase in evaporator
capacity as well as the reduction in compressor work should be utilized. Since the
efficiency of the heat pump is defined as evaporator capacity over net compressor
power input, this parameter is improved by two contributions.
The benefit of using the expander depends strongly on the overall efficiency of
the device. Current designs reach an overall efficiency gain of the heat pump on the
order of 5%. When refrigerant mixtures are used, the expander causes the evaporator
inlet temperature of the refrigerant to be reduced, an additional benefit.
4.5 THE THREE-PATH EVAPORATOR

The three-path evaporator offers a unique opportunity for zeotropic mixtures not
available for pure fluids. Its effectiveness depends strongly on the presence of a large
glide. Figure 4.5.1 demonstrates how the concept works. The first path in the
evaporator is for the chilled fluid, here assumed to be water. The second path is for
the evaporating refrigerant mixture and both paths are best arranged in counter flow.
The third path is for the high pressure liquid refrigerant that leaves the condenser
(or, as an alternative, exits the suction line to liquid line heat exchange, not shown
in Figure 4.5.1). With this internal heat exchange process, the evaporating refrigerant
mixture cools the water as well as the liquid refrigerant. Because of the second heat
source, the cooling capacity of the evaporating refrigerant seems to be reduced.
However, at the same time the enthalpy of the liquid refrigerant is reduced by the
same amount; in terms of cooling capacity, there is no net effect. Nevertheless, when
mixtures are used, this measure leads to a reduced temperature at the evaporator inlet.
The glide is increased as well if the pressure level is constant, demonstrated in Figure
4.5.2. The net effect is very similar to increasing the degree of subcooling at the
condenser outlet, as shown in Figure 4.1.2. However, in that case the evaporator
Condenser
Compressor
Three Path Evaporator
Water
FIGURE 4.5.1 Three-path evaporator.

T5a < T5
ln (P)
T5a T5
4a 4
New Process Line

w/Subcooling
5 Increase in
5a
Suction Pressure
FIGURE 4.5.2 The three-path evaporator lowers the evaporator inlet temperature. Alterna-
tively, the suction pressure can be raised.
capacity is increased and the inlet temperature lowered, also beneficial for pure
fluids. In the case of the three-path heat exchanger, no benefit is derived for pure
fluids because there is no net gain in evaporator capacity while there is a reduction
in the evaporator inlet temperature of the two-phase refrigerant stream for mixtures.
As discussed above, this benefit again can be translated into a somewhat higher
compressor suction pressure when the conditions in the evaporator allow. This
condition is fulfilled when the evaporator outlet temperature after the increase in
suction pressure is still lower than the incoming water temperature.
The main difference between improved subcooling at the condenser outlet and
the three-path evaporator is the following: When the liquid refrigerant is subcooled
in the condenser, the heat of subcooling is rejected to the exterior where it leaves
the cycle. With the three-path evaporator, the heat of subcooling remains within the
cycle. Therefore, no capacity benefit is achieved but a secondary benefit (reduced
evaporator inlet temperature) is acquired in the case of zeotropic mixtures. The
benefit of the three-path evaporator is available in addition to that of the suction to
the liquid line exchanger and there is no operational penalty associated with it.
Ideally, and especially for mixtures with high specific heat capacities, a designer
should consider employing all three measures to the maximum beneficial extent: sub-
cooling, suction line to liquid line exchange and the three-path evaporator configuration.
REFERENCES
Domanski, P.A., 1995, “Theoretical Evaluation of the Vapor Compression Cycle With a
Liquid-Line/Suction-Line Heat Exchanger, Economizer, and Ejector,” NIST Report,
NISTIR 5606.
Radermacher, R., 1988, “Vapor Compression Heat Pump with Non-azeotropic Refrigerant
Mixture and Absorber Desorber Heat Exchange,” U.S. Patent No. 4,724,679.
Radermacher, R. and D.S. Jung, 1993, U.S. Patent No. 5,207,077.
Vakil, H.B., “Means and Methods for the Recovery of Expansion Work in Vapor Compression
Cycle; Subcooling in Tube Parallel to Evaporator,” U.S. Patent No. 4,304,099.
Vakil, H.B., “Vapor Compression Cycle Device with Multicomponent Working Fluid Mixture;
Receiver Behind Condenser and in Between the Two Evaporators,” U.S. Patent No.
4,283,919.
Vakil, H.B., “Vapor Compression Cycle Device with Multicomponent Working Fluid Mixture
and Method; Receivers Behind Condenser and Evaporators,” U.S. Patent No.
4,217,760.
Vakil, H.B. and J.W. Flock, “Vapor Compression Cycle Device with Multicomponent Working
Fluid Mixture and Method; Pseudo Counter Flow Heat Exchanger,” U.S. Patent No.
4,281,890.
Vakil, H.B., “Vapor Compression Cycle Device with Multicomponent Work Fluid Mixture;
Receiver and Separate Separation Device Behind Cond. Accumulator,” U.S. Patent
No. 4,179,898.

5 Experimental
Performance
Measurements
Section 3.6 outlines the Lorenz cycle and its potential for improved efficiency under
properly selected operating conditions. These occur in a heat pump application when
there is a large and approximately equal temperature glide in condenser and evap-
orator and a temperature lift that is as small as possible as compared to the glide.
One such application is air-conditioning, where for most operating hours the air
temperatures inside and outside a building are essentially equal. An ARI Standard
210/240 (1994) specifies the return air temperature in a building as 26.7˚C and the
outdoor temperature as 27.8˚C. In order to ensure adequate dehumidification, the
air supplied to the inhabited space must be cooled to about 12.8˚C. Thus, the
temperature glide in the evaporator is 14 K. Accordingly, the temperature glide in
the condenser should be at least 14 K or even more as described in Section 3.8; here
it is chosen to be 19 K. Figures 3.8.1 and 3.8.2 show a schematic of the temperature
conditions involved.
Although the air stream temperatures reflect almost the ideal operating condi-
tions (it would be better if both air streams would start from the same temperature),
the situation is not quite so ideal for the refrigerant. Since there is always a final
approach temperature for a realistic heat exchanger, the lowest temperature of the
refrigerant leaving the condenser and the warmest leaving the evaporator are more
than 1 K apart. To demonstrate this performance potential, a key experiment is
described in this chapter. It will be discussed here in considerable detail because it
highlights opportunities and challenges of working fluid mixtures very clearly. The
experimental setup is also a very good example for how reliable heat pump tests
can be conducted with the necessary checks and redundancy to ensure reliable test
data. In this regard, this chapter introduces experimental evaluation of refrigerant
mixtures in a laboratory breadboard and actual heat pump systems. Some of exper-
imental results of refrigerant mixtures using these test facilities are then explained
(Vineyard, 1988; Vineyard and Conklin, 1991; Conklin and Vineyard, 1991; Vine-
yard, Conklin, and Brown, 1993; Kauffeld et al., 1990; Pannock and Didion, 1991).
5.1 LABORATORY BREADBOARD TESTS

In this section, three sets of experimental investigations are introduced on the
performance of mixtures using laboratory breadboard heat pumps conducted at NIST
(Kauffeld et al., 1990; Pannock and Didion, 1991) and ORNL (Vineyard, 1988;
149

Vineyard and Conklin, 1991; Conklin and Vineyard, 1991; Vineyard, Conklin, and
Brown, 1993).
5.1.1 NIST BREADBOARD HEAT PUMP I

The following text is based on excerpts of the above mentioned report. The full text
is available as NISTIR 90-4290.
5.1.1.1 Test Facility
The breadboard heat pump I is shown schematically in Figure 5.1.1. Water was
selected as a heat source- and sink-fluid because capacity measurements are simple
and because counterflow and intracycle heat exchange can be achieved. A constant
evaporator heat flux was desired to compare the different refrigerants (McLinden
and Radermacher, 1987). Because the refrigerants to be examined had differing
properties, achieving this goal required use of a variable speed compressor. An open
two piston reciprocating compressor was selected together with a variable speed
motor.
Figure 5.1.2 shows a side view of the setup. The condenser heat exchangers are
coiled aluminum extrusions, as shown in Figure 5.1.3. The evaporator heat exchang-
ers (Figure 5.1.4) were chosen to allow for temperature measurements all along the
flow channel. Two 6 m long extruded copper tubes were selected for the evaporator
heat exchanger. The heat exchanger tubes consisted of only two passages, a center
path with “microfins” on the walls and a set of “rectangular” channels around this
inner tube. The fins and channels are spiraled, changing top to bottom every 150
mm. A third passage was added on the outside of the evaporator to obtain a heat
exchanger for a third fluid, thus allowing for heat exchange between the evaporator
refrigerant and the condensed liquid refrigerant throughout the length of the evap-
orator. The two heat exchanger tubes are connected in series, resulting in a total
evaporator heat exchanger length of 12 m.
Thermocouples were soldered to the outside of the evaporator heat exchangers
every 0.6 m, thereby allowing measurement of the temperature profile in the outer-
most channel. For the rectangular channels, measurement was limited to the crossover
between 3 m sections of the 12 m heat exchanger. This resulted in five thermocouples
for these passages. For the center passage, thermocouples are located every 0.6 m
in a sealed 3.2 mm thin wall, stainless steel tube. These thermowells are mounted
in the center of the innermost channel to measure the in-stream temperature of the
flowing fluid. Additional measurement devices were several other thermocouples,
thermopiles and pressure transducers located at critical points in the cycle.
Another important feature of the breadboard heat pump is a liquid/vapor-sepa-
rating accumulator in front of the compressor serving as a refrigerant storage vessel
as well (Figure 5.1.5).
5.1.1.2 Capacity Measurements
The capacity of both heat exchangers was measured using redundant methods for
verification and the compressor power was measured using a torque meter and

Chilled Water
T1
.
Q1 T2
.
m1
T4
Condenser Pump Refrigerant
T3
T6, P9
Flow Meter Water/Glycol
T5, P5
.
Oil Separator Electric Heater
m2 T7, P7
T9, P9 Compressor Motor

Torque
T10
. .
Meter
Evaporator Condenser Capacity:
P10 T8, P8
. .
Qcond = m1 Cp (T4−T3)
T11 T12 . .
Qcond = Q1 (T4−T3)/(T1−T2)
Qcond = m2 (h5−h6)
.
m 3
. . = Q. + Q. + Q.
Evaporator Capacity:
Qpump . = m. C (T − T )
Qevap 2 pump calor
. = m. (hp −h )
Q2
Qevap 3 12 11
T13 . = Q. (T − T )/(T
Qevap 2 10 9
Qevap 2 12 11 13 − T11)
Evaporator Calorimeter . = torque × rpm

Compressor Power:
Enclosure . = m. (h − h )
Qcomp
. . = Q. −Q.
Q
Q
comp 2 7 8
Qcalor comp cond evap
FIGURE 5.1.1 Schematic of breadboard heat pump I (Kauffeld et al., 1990).

FIGURE 5.1.2 As-built drawing of breadboard heat pump I (Kauffeld et al., 1990).
FIGURE 5.1.3 Schematic of condenser heat exchanger (Kauffeld et al., 1990).
FIGURE 5.1.4 Schematic of evaporator extruded heat exchanger (Kauffeld et al., 1990).

Experimental Performance Measurements 153
Wet Dry
Vapor Vapor
A A
Section A-A
Liquid
Oil Return
FIGURE 5.1.5 Schematic of accumulator (Kauffeld et al., 1990).
tachometer. All the different methods employed throughout the test program agreed
closely (within 6%), confirming the validity of the test results.
5.1.1.3 Test Procedure
Two zeotropic binary refrigerant mixtures R22/R114 and R13/R12 were tested in
the breadboard heat pump. Tests were conducted at the same capacity for each
mixture to achieve equal average heat flux per unit area of the heat exchangers for
all tests as one of the major criteria for comparability of refrigerants. One exception
was pure R114, which would have required an excessively high compressor speed
to reach the desired capacity. The capacity was chosen to be 4.1 kW, obtained with
pure R22 at 500 RPM compressor speed. Heat sink and heat source entry and exit
water temperatures were kept constant for all tests as the second major criterion for
comparability (McLinden and Radermacher, 1987). The temperatures were 28 and
47˚C entering and leaving the condenser, and 27 and 13˚C entering and leaving the
evaporator. The expansion device was set simultaneously to give marginal subcooling
at the condenser outlet and to provide evaporation throughout the entire evaporator.
The subcooling was determined by the disappearance of vapor bubbles in a sight
glass in the liquid line upstream of the expansion valve. The condition of flooded
evaporator was determined by the presence of liquid droplets leaving the evaporator
in a sight glass in this pipe and by the presence of liquid in the accumulator.
The mixture mass fractions examined cover the whole range from 0 to 100%
for the R22/R114 test series, whereas for the second refrigerant mixture (R13/R12)
mass fractions were limited to less than 45% of R13 by weight because of excessive
pressures in the condenser that exist with more R13.

TABLE 5.1
Evaporator Configurations
Configuration No. 1 2 3 4
Evaporating Refrigerant C B A A
Liquid Refrigerant B C B C
Water A A C B
A: inside, B: rectangles, C: outside
Source: Kauffeld et al., 1990.
5.1.1.4 Heat Exchanger Variations
A major task of this project was to analyze the influence of different heat exchangers
on the performance of a heat pump employing zeotropic refrigerant mixtures. Four
different configurations of the three passages in the evaporator were tested. Detailed
instrumentation and observation are limited to the evaporator because this heat
exchanger has a greater effect on system performance than the condenser. According
to the nomenclature of Figure 5.1.4, the four evaporator configurations are shown
in Table 5.1.
Configurations 2 and 4 were expected to perform better than 1 and 3 since the
evaporating refrigerant and water (which constituted the majority of the transferred
heat) were in the channels that had enhanced surfaces. Furthermore, these channels
were adjacent, limiting the losses due to heat passing through the intermediate
passage.
The performance of configurations 1 and 3 is strongly influenced by the surface
characteristic of the outermost channel. The smooth copper surface provides a poor
heat exchange area, resulting in large temperature differences between the water and
the refrigerant for these two configurations. The relative heat exchanger performance
is shown in the temperature plots for the four configurations for pure R22 in Figure
5.1.6. It is observed that R22 uses the full length of the heat exchanger for config-
urations 1 and 3 but only about one half to three quarters of the heat exchanger for
configurations 2 and 4. Figure 5.1.7 shows the evaporator temperature profiles of
R22/R114. As shown, the heat exchangers for configurations 2 and 4 have smaller
approach temperatures than that of R22 due to the temperature glide of R22/R114.
Figures 5.1.8 and 5.1.9 show the performance of R22/R114.
For the mixture of R22/R114, a maximum increase in coefficient of performance
(COP) of 32% was found at a mass fraction of 65% of R22. At lower R22 mass
fraction, the capacity dropped off rapidly and the COP of R114 was determined to
be about 40% lower than that of R22. However, this large decline is a reflection of
the fact that the compressor is not designed for such a low-pressure refrigerant and
valve pressure losses become dominant. For R22/R114 there is no significant dif-
ference in performance whether or not the suction-line heat exchanger is used (Figure
5.1.8). The best performance was achieved with evaporator configuration 4. Config-
uration 3 performed worst but still showed an increase in performance of 5 to 10%.

90 90
30 30
Water Water
Refrigerant Refrigerant
75 75
Temperature, °C
Temperature, °C
Temperature, °F
Temperature, °F
20 20
60 60
10 10
45 45
C.O.P = 4.81 C.O.P = 5.15
30 0 0
30
Distance Through Evaporator Distance Through Evaporator
(a) Configuration 1. (b) Configuration 2.
90 90
30 30
Water Water
Refrigerant Refrigerant
75 75
Temperature, °C
Temperature, °C
Temperature, °F
Temperature, °F
20 20
60 60
10 10
45 45
C.O.P = 4.85 C.O.P = 5.18
30 0 0
30
(c) Configuration 3. (d) Configuration 4.
FIGURE 5.1.6 Evaporator temperature profiles for R22 (Kauffeld et al., 1990).

90 90
30 30
Water R22/R114 (73/27) Water R22/R114 (57/43)
Temperature, °F
Temperature, °C
Temperature, °F
Temperature, °C
75 Refrigerant 75 Refrigerant
20 20
60 60
10 10
45 Refrigerant glide = 8.4°F 45 Refrigerant glide = 16.3°F
C.O.P = 5.78 C.O.P = 5.02
0 0
30 30
(a) Configuration 2, best COP. (b) Configuration 2, best glide.
90
30 90 R22/R114 (57/43) 30
Water R22/R114 (75/25) Water
Temperature, °F
Temperature, °C
Temperature, °F
Temperature, °C
20 20
60 60
10 10
45 45
Refrigerant glide = 14.5°F Refrigerant glide = 25.1°F
C.O.P = 5.42 0 C.O.P = 4.91 0
30 30
(c) Configuration 3, best COP. (d) Configuration 3, best glide.
90 90
30 30
Water R22/R114 (66/34) Water R22/R114 (60/40)
Temperature, °F
Temperature, °C
Temperature, °F
Temperature, °C
20 20
60 60
10 10
45 Refrigerant glide = 18.9°F 45 Refrigerant glide = 23.3°F
C.O.P = 5.80 C.O.P = 5.80
0 0
30 30
(e) Configuration 4, best COP. (f ) Configuration 4, best glide.
FIGURE 5.1.7 Evaporator temperature profiles for R22/R114 (Kauffeld et al., 1990).
Figures 5.1.10 and 5.1.11 show the performance of R13/R12. The improvement
in cycle efficiency for the mixture R13/R12 compared to the efficiency obtained
with pure R22 and pure R12 is shown in Figure 5.1.11 to be 16 and 40%, respectively,
with internal heat exchange and 8 and 27%, respectively, without internal heat
exchange. For the test set performed with R13/R12, it was not possible to perform
tests with high concentrations of R13 since the pressure would have been far beyond
the highest acceptable pressures.
Another observation is that at any temperature glide less than the maximum
possible, there will be two mass fractions that will give the required glide. The
choice of which of these two mass fractions to use would be based on other
refrigerant properties. For instance, with the R22/R114 mixture, the composition
high in R22 would be chosen because of the better compressor efficiency and
capacity with higher R22 mass fractions. With the R13/R12 mixture, the mass
fraction low in R13 would be chosen to avoid the high discharge pressures with
high mass fractions of R13.

R22/R114
6
C.O.P.
5
W/O liquid line HX
Configuration 2
W/O liquid line HX
4 Configuration 3
W/O liquid line HX Configuration 4
With liquid line HX Configuration 2
3
100 80 60 40 20 0
Weight % R22
FIGURE 5.1.8 Performance of R22/R114 for evaporator configurations 2, 3 and 4 (Kauffeld

et al., 1990).
7
R22/R114
6 32%
C.O.P.
4
With liquid line heat exchanger
Without liquid line heat exchanger
3
100 80 60 40 20 0
Weight % R22
FIGURE 5.1.9 Performance of R22/R114 for evaporator configuration 4 (Kauffeld et al.,

1990).
The capacity per compressor revolution for both mixtures in evaporator config-
uration 4 is shown in Figure 5.1.12. Compared to pure R22, the R22/R114 mixture
(65/35 wt.%) that showed 32% efficiency improvement (Figure 5.1.10) resulted in
a capacity loss of 8%. The R13/R12 mixture (34/66 wt.%) that showed a 16%
efficiency improvement over pure R22 (Figure 5.1.11) resulted in a capacity increase
of 21%.
5.1.1.5 Linearity of the Enthalpy vs. Temperature Relationship
An interesting feature of temperature plots is that the location of the pinch points
varies for different refrigerant mixtures. The pinch point, the closest temperature

6 R13/R12 4
Without liquid line HX
Configuration 2
Without liquid line HX
4
C.O.P.
5 Configuration 4
With liquid line HX
3
Configuration 2
With liquid line HX
Configuration 3 2
4 With liquid line HX 2
Configuration 4
100 80 60 40 20 0
Weight % R13
FIGURE 5.1.10 Performance of R13/R12 for evaporator configurations 2, 3 and 4 (Kauffeld

et al., 1990).
7
With liquid line heat exchanger
Without liquid line heat exchanger
6
C.O.P.
16%
C.O.P. for R22 8%
5
40% 27%
R13/R12
4
100 80 60 40 20 0
Weight % R13
FIGURE 5.1.11 Performance of R13/R12 for evaporator configuration 4 (Kauffeld et al.,

1990).
0.70
Volumetric Capacity, Btu/Revolution
0.60 R1
3/
R1
0.50 2
0.40 R22
/ R1
14
0.30
0.20
0.10
0
100 90 80 70 60 50 40 30 20 10 0
Weight % Low Boiler (R22 or R13)
FIGURE 5.1.12 Volumetric capacity of R22/R114 and R13/R12 for evaporator configuration
4 (Kauffeld et al., 1990).

90
R22/R114 (66/34)
Water
75 Refrigerant
Temperature, °F
60
45
30
90
R13/R12 (32/68)
Water
75 Refrigerant
Temperature, °F
60
45
30
Distance Through Evaporator
FIGURE 5.1.13 Comparison of evaporator temperature profiles for R22/R114 and R13/R12
(Kauffeld et al., 1990).
approach between the refrigerant and the heat exchange fluid, is at the two ends of
the heat exchanger for the R22/R114 mixture, whereas for the R13/R12 mixture the
pinch point is in the center of the heat exchanger. This is shown in Figure 5.1.13,
where a line connects the points of entry and exit to emphasize this nonlinearity.
The nonlinear shape of the temperature profile during evaporation results from
the differing properties of the pure refrigerants in combination with mixture effects.
The dominant effect in determining the shape of the profiles appears to be the relative
amounts of the more and less volatile components. With the R22/R114 mixture of
60% R22, the bulk of heat necessary to vaporize the mixture is required at temper-
atures close to the bubble point temperature (i.e., at temperatures closer to the boiling
point of the more volatile R22). As a result, the temperature versus enthalpy profile
is concave. With the R13/R12 mixture, the mass fraction of the more volatile R13
is only 20% and thus the bulk of the heat of vaporization is concentrated at the
higher temperatures, resulting in a convex profile.
A secondary effect is the different heats of vaporization for the two components.
This is most pronounced with R22/R114, where the heat of vaporization of R22 is
substantially higher than that of R114. Because the first bubbles of vapor generated
are enriched in R22, the higher heat of vaporization for this refrigerant further
contributes to the concave shape. This behavior is important for the prediction of
system performance by the use of simple computer programs which assume a linear
temperature glide throughout the heat exchanger, since the actual glide may deviate
quite far from linearity. These errors are greatest with efficient heat exchangers where

the temperature differences are small, the application seen as most favorable to
mixtures.
The convex shape of the temperature profile of R13/R12 tends to be amplified
by a pressure drop as present in the evaporator, whereas the concave shape of
R22/R114 tends to be leveled. Another aspect of this nonlinearity is discussed in
the next section.
5.1.1.6 Liquid Precooling in Evaporator
The final part of this investigation was concerned with the validity of the proposed
improvement obtained by using an intermediate heat exchange between the evapo-
rating refrigerant and the condensed liquid (Vakil, 1981). Liquid precooling in
evaporator (LPE) improves efficiency with mixtures by shifting a portion of the
evaporator capacity to a lower vapor quality and thus to a lower temperature. Tests
have been conducted with both refrigerant mixtures R22/R114 and R13/R12 to
evaluate this theoretical proposal. As one can see from Figures 5.1.10 and 5.1.11,
noticeable improvement in efficiency is only obtained for the mixture of R13/R12.
The reasons for this different behavior are seen in the pressure-enthalpy diagrams
for the two refrigerant mixtures.
First, the two-phase isotherms are nearly flat at low quality for R22/R114 (Figure
5.1.14) while those for R13/R12 (Figure 5.1.15) show a substantial slope throughout
the two-phase region. Because of this flatness, the heat exchanger has little value
Enthalpy (Btu/lbm)
25 50 75 100 125 150
10,000
5000 750
100°
80°
Pressure (kPa)
2000 60° 300

Pressure (psia)
40°
1 4,4'
1000 1' 150
20°
2' 3,3'
2 75
500
s = 0.2 kJ/kg°C
0°
.2
0.4
=0
0.4
0.6
0.6
ty
0.8
ali
0.8
Qu
−20° 30
200
50 100 150 200 250 300
Enthalpy (kJ/kg)
FIGURE 5.1.14 Effect of suction line heat exchanger for R22/R114 (Kauffeld et al., 1990).

Enthalpy (Btu/lbm)
25 50 75 100 125 150
10,000
5000 750
60°
1' 1
4, 4'
Pressure (psia)
Pressure (kPa)
40°
2000 300
2' 20°
3'
2 3
s = 0.4 kJ/kg°C
10000 150
0°
0.6
0.8
75
0.2
500 −20°
y=
0.4
alit
0.6
Qu
0.10
0.8
200 30
50 100 150 200 250 300
Enthalpy (kJ/kg)
FIGURE 5.1.15 Effect of suction line heat exchanger for R13/R12 (Kauffeld et al., 1990).
for R22/R114 for the same reasons that cause it to have little value for pure refrig-
erants with their truly horizontal isotherms. Referring to Figures 5.1.14 and 5.1.15,
the shift of the evaporator entering condition from point 2 to 2 can be seen to result
in a higher evaporator pressure (which improves efficiency) at the same average
evaporator temperature for R13/R12, while the shift from point 2 to 2 has no effect
on evaporator pressure for R22/R114. Second, the shape of the two-phase dome
results in flashing more of the R13/R12 mixture between the approximate operating
points (30˚C condensing, 10˚C evaporating) at which the tests were run, indicating
more potential for reducing entering vapor quality.
5.1.1.7 Discussion
By using zeotropic refrigerant mixtures with their changing temperatures at constant

pressures in the two-phase region, one can obtain a temperature glide on the refrig-
erant side in a conventional heat exchanger. A zeotropic mixture at the right mass
fraction can match the temperature glide of the heat exchange fluid in a counter flow
heat exchanger.
However, special care must be taken in the heat exchanger design to suit the
requirements of the zeotropic mixtures. This is one of the reasons why several earlier
experimental studies failed to show the projected improvements. Because pure
refrigerants quickly encounter a pinch point as the heat exchanger area is increased,
mixtures can take much better advantage of increased areas. For instance, with the
most effective heat exchanger configuration, the pure refrigerant could only effec-
tively use a quarter of the heat exchanger area because of its pinch point and would
be expected to produce substantially the same efficiency with its heat exchangers

reduced in size to a quarter of that employed. It must be emphasized, however, that

all the comparisons between pure and mixed refrigerants presented in this chapter
are for equal areas. A compromise must be found for each application between
increased cost for the heat exchangers and obtainable improvements in efficiency,
resulting in cost savings when operating the system. Furthermore, the heat exchanger
should not result in a high pressure drop since the pressure drop affects the temper-
ature glide of a mixture.
Finally, the proposed improvements in cycle efficiency by the introduction of
an internal heat exchange between the evaporating refrigerant and the condensed
liquid is proven valid. The amount of improvement is dependent on the shape of the
vapor dome and temperature profiles and can be small for some mixtures. It is also
shown that the introduction of such a heat exchanger does not significantly affect
the cycle efficiency of single component systems. The potential for cycle improve-
ment is present with mixtures. Employing zeotropic refrigerant mixtures results in
an efficiency improvement of as much as 32% over R22 when heat exchangers and
temperature glides are selected properly.
5.1.1.8 Conclusion
• For all heat exchanger configurations for which a full range of mass
fractions was tested, the optimum mass fraction of each mixture performed
better than pure R22.
• The best efficiency measured with the mixture R22/R114 (at a mass
fraction of 65% R22) was approximately 32% higher than the best effi-
ciency measured with R22.
• The best efficiency measured with the mixture R13/R12 (at a mass fraction
of 35% R13) was approximately 16% better than the best efficiency
measured with R22.
• The better the heat exchanger effectiveness, the greater the improvement
the mixtures showed over pure R22.
• In the evaporator configurations having poorer heat exchanger effective-
ness, the gliding temperature effect of mixtures was less important to
cycle efficiency than other refrigerant properties.
• Pressure drop in the evaporator reduced the temperature glide and hence
reduced the cycle efficiency improvement by mixtures.
• Nonlinearity of temperature with enthalpy was observed for the two mix-
tures tested.
• Intracycle heat exchange between the condensed liquid and evaporating
refrigerant streams benefited the R13/R12 mixture but not the R22/R114
mixture.
• Intracycle heat exchange between the condensed liquid and evaporating
refrigerant streams is beneficial for those mixtures showing a substantial
loss of potential temperature glide as a result of flashing through the
expansion device.
• Efficiency improvement by using mixtures does not imply loss of capacity
as a trade-off.

5.1.2 NIST BREADBOARD HEAT PUMP II

The following text is based on excerpts of an NIST internal report. The full text is
available in NISTIR 91-4748.
The laboratory breadboard heat pump II was designed for a 3.5 kW capacity.
Other design criteria were:
• Counterflow heat exchanger configuration for condenser, evaporator and

suction line heat exchanger (SLHX).
• Liquid heat transfer fluid.
• Variable speed compressor.
• System can be operated with or without SLHX.
• Accessibility of refrigerant and heat transfer fluid in order to obtain
condenser and evaporator temperature profiles.
Figure 5.1.16 shows a schematic of the laboratory breadboard heat pump II. The
refrigerant side consists of the compressor, condenser, SLHX, expansion device and
evaporator. To minimize the charge, the system components were limited to the basic
components without any large volume auxiliary equipment such as an oil separator
or an accumulator. The compressor was two cylinder reciprocating compressor. All
heat exchangers used in this breadboard heat pump II (evaporator, condenser and
SLHX) were in a counterflow heat exchange configuration: the refrigerant flows in
the inner tube and a water-ethylene glycol mixture flows in the annulus. The inner
tube and annulus side were equipped with turbulators and spine fins in order to
increase the heat transfer coefficient. This heat transfer enhancement resulted in
large flow pressure drops but had other benefits such as the compactness of the
system design and reduced refrigerant charge. The SLHX was installed between the
liquid line after the condenser outlet and compressor suction line with a bypass line.
The expansion valve was a metering valve controlled manually.
5.1.2.2 Test Results of Test Apparatus II
For all tests, two cycle parameters were controlled such that the degree of subcooling
at the condenser outlet and degree of superheating at the evaporator outlet were
positive in order to get comparable test results. The degree of subcooling was
especially limited as much as possible (not greater than 2 K) and the superheating
region was limited within 5% of the evaporator length. These conditions were
satisfied by adjusting the refrigerant charge and expansion valve opening. The
capacity was maintained for all tests by adjusting the compressor speed from
1500 RPM to 1620 RPM. A refrigerant sample was taken from the discharge line
during the steady state phase of the test and then evaluated with the gas chromato-
graph to measure the mass fraction of the mixtures.
Using this test apparatus II, R32/R134a and R32/R152a mixtures at various mass
fractions of R32 were conducted at various test conditions defined in Table 5.2.

HC
T
W/G
FM MM
C T P
M S Co
Cooling
Brine
I X
Charging
System
IX
Three-way W/G
valve
Thermostatic P
T T
valve, dioxide T
T Thermostatic T E
valve FM MM
Hand valve
HC HV
Filter, dryer
(interground) C - Condenser HC - Heater, constant P - Pump
CO - Compressor HV - Heater, water S - Longer & speed motor
Sight glass E - Evaporater I - Inverter W/G - water/glycol tank
FM - Volume flow meter IX - Inverter heat exchanger X - External heat exchanger
Filter (water) MM - Mass flow meter M - Mirror
FIGURE 5.1.16 Schematic of breadboard heat pump II (Pannock and Didion, 1991).

TABLE 5.2
Test Conditions for Heat Transfer Fluid
Evaporator Evaporator Condenser Condenser
Test Inlet (˚C) Outlet (˚C) Inlet (˚C) Outlet (˚C)
High temperature cooling (A) 26.7 14.4 35.0 43.2

Low temperature cooling (B) 26.7 14.4 27.8 43.2
High temperature heating (47S) 8.3 14.4 21.1 43.2
Low temperature heating (17L) 8.3 14.4 21.1 43.2
Source: ASHRAE, 1995.
High Temperature Cooling Test (Test A)

The cooling capacity was kept constant at 3.5 kW for these tests. The compressor speed
of R32/R134a and R32/R152a was the same as that of R22 when the mass fractions
of R32/R134a and R32/R152a are at 24/76 wt.% and at about 31/69 wt.%, respectively.
Figure 5.1.17 shows the COP improvement over R22 for Test A. The COP improvement
increases steadily when the R32 mass fraction increases for both mixtures. For R32
mass fraction below 22% in the R32/R134a mixture, the COP is lower than that of
R22. The maximum COP improvement reached at 19% over R22 at 40% of R32 mass
fraction. For R32/R152a, the COP is higher than that of R32/R134a for mass fractions
lower than about 37%. The maximum COP increase was 17 to 18% over that of R22
at the same capacity. The COP was 14 and 4% higher for R32/R152a and R32/R134a,
respectively, at the mass fraction having the same speed and capacity with R22.
25
20
COP improvement over R22 (%)
15
10
R32/R152a R32/R134a
−5
−10
0.15 0.2 0.25 0.3 0.35 0.4 0.45
Mass fraction R32
Test condition 1A
FIGURE 5.1.17 Cooling COP for Test A (Pannock and Didion, 1991).

The R32 mass fraction of the mixture affects the suction and discharge pressure.
Lowering R32 mass fraction can reduce the operating pressures but it also reduces
volumetric capacities. R32/R152a mixtures showed lower pressures than R32/R134a
mixtures at the same R32 mass fraction. At a mass fraction of 28 and 36%, the
suction pressures of R32/R134a and R32/R152a are equal to that of R22. A similar
trend to the suction pressures was observed for the discharge pressures. The discharge
pressures of R32/R134a and R32/R152a vary from –12 to +8% and from –24 to
–6% with respect to R22 in the measured mass fraction range, respectively.
For both mixtures, the suction temperature was constant (within ±1 K) for all
tests but the discharge temperature was different. For both mixtures, the discharge
temperature was lower than that of the R22. The R32/R152a mixtures showed a
decrease of 3 K to 5 K with increasing R32 mass fraction and the R32/R134a mixture
showed a decrease of 5 K to almost 10 K as compared to R22.
The operating pressures and temperatures of both mixtures are within acceptable
ranges as expected from the test condition.
Low Temperature Cooling Test (Test B)
The cooling capacity was kept constant at 3.7 kW for these tests. Figure 5.1.18
shows the COP improvement over R22 for Test B. Figure 5.1.18 shows that the COP
improvement increases steadily when the R32 mass fraction increases for both
mixtures as similar to Test A case.
For R32 mass fraction below 17% in the R32/R152a mixture, the COP is lower
than that of R22. The COP improvement was over 20% when the R32 mass fraction
30
20
R32/R152a R32/R134a
10
−10
−20
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Mass fraction R32
Test condition 1B
FIGURE 5.1.18 Cooling COP for Test B (Pannock and Didion, 1991).

was higher than 35%. For R32/R134a, the COP is lower than that of R32/R152a for
R32 mass fractions lower than about 30%. The maximum COP increase was 22%
over that of R22 at the same capacity at 38% R32 mass fraction.
At a mass fraction of 28 and 36%, the suction pressures of R32/R134a and
R32/R152a are equal to that of R22. A similar trend to the suction pressures was
observed for the discharge pressures. The discharge pressures of R32/R134a and
R32/R152a vary from –12 to +8% and from –24 to –6% with respect to R22 in the
measured mass fraction range, respectively.
Similar to Test A, the suction and discharge pressures were again within accept-
able limits with respect to R22. The suction pressures of the R32/R134a mixture
were 10 to 15% higher than those of the R32/R152a mixture, meaning about 100 kPa
higher suction pressure. The discharge side pressure difference was about doubled
to 200 kPa. The discharge pressures of R32/R134a were lower than those of R22
for R32 mass fraction of less than 30%. For R32/R152a, all measured discharge
pressures were below that of R22.
For both mixtures, the suction temperature was constant (within ±1 K) for all
tests except one data point but the discharge temperature was different. For both
mixtures, the discharge temperature was lower than that of the R22. The R32/R152a
mixtures showed a decrease of 3 to 5 K for 20 to 30% of R32 mass and the
R32/R134a mixture showed a decrease of 10 K with more than 30% R32 mass
fraction.
High Temperature Heating Test (Test 47S)
The heating capacity was kept constant at 3.1 kW for these tests. Figure 5.1.19
shows the COP improvement over R22 for Test 47S. Again, the COP improvement
increases steadily when the R32 mass fraction increases for both mixtures as similar
to the cooling mode. Different from the cooling mode, the heating COPs of the
R32/R134a mixtures were higher than those of the R32/R152a mixtures (Figure
5.1.20). The COPs of both mixtures were higher than that of R22 when the R32
mass fraction was more than 20%. The R32/R152a mixture also shows a COP
improvement against R22 when the R32 mass fraction was more than 20%. At the
mixture compositions of same speed and same capacity, R32/R134a and R32/R152a
showed 4 and 8% improvement, respectively.
Low Temperature Heating Test (Test 17L)
The heating capacity was kept constant at 2.0 kW for these tests. Figure 5.1.20
shows the COP improvement over R22 for Test 17L similar to the Test 47S case.
The COP improvement increases steadily when the R32 mass fraction increases for
both mixtures, as with the other cases. Similar to Test 47S, the heating COPs of the
R32/R134a mixtures were 5 to 10% higher than those of the R32/R152a mixtures
at the same R32 mass fraction (Figure 5.1.20). The COPs of both mixtures were
lower than that of R22 for most of the R32 mass fractions investigated. Only the
R32/R134a mixture showed a 5% COP improvement against R22 at 40% of R32
mass fraction. The same COP as R22 was reached at about 30% of R32 mass
fractions for the R32/R134a mixtures and at above 40% of R32 mass fractions for
the R32/R152a mixtures.

15
10
5 R32/R152a
R32/R134a
0
−5
−10
−15
−20
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Mass fraction R32
Test condition 1B
FIGURE 5.1.19 Heating COP for Test 47S (Pannock and Didion, 1991).
10
5
R32/R134a
−5
−10
R32/R152a
−15
−20
−25
−30
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Mass fraction R32
Test condition 10
FIGURE 5.1.20 Heating COP for Test 17L (Pannock and Didion, 1991).

25
20
15
R32/R152a
10
5
R327/R134a
−5
−10
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Mass fraction R32
Test condition 1A-SLHX
FIGURE 5.1.21 Cooling COP for Test SLHX (Pannock and Didion, 1991).
Suction-Line Heat Exchange Test (Test SLHX)

The SLHX was tested at the same operating conditions as Test A (high temperature
cooling). For a fair comparison, R22 was also tested with a SLHX and used as a
reference. The cooling capacity was kept constant at 3.5 kW for these tests. Figure
5.1.21 shows the COP improvement over R22 for Test SLHX. The COP improvement
increases steadily for both mixtures when the R32 mass fraction increases. For
R32/R134a mixtures, the COP of R32/R134a matched the COP of R22 at 20% of
R32 mass fraction and the COP was 17% higher than R22 at 40% of R32 mass
fraction. For R32/R152a, the COP improvement was similar to R32/R134a except
for the R32 mass fractions over 35%.
Overall, the SLHX provided a performance improvement, 4% in COP for
R32/R152a and 5.8% in COP for R32/R134a. However, lower compressor speeds
were used to run at the same capacity. This might contribute to the better compressor
efficiency and COP improvement. If the compressor speed is the same as with R22,
the COP improvement of the R32/R134a mixture and R32/R152a mixture was 3
and 11%, respectively, at the R32 mass fraction of the same capacity with R22. The
use of the SLHX resulted in a lower refrigerant mass flow rate at the same capacity
since the latent heat of evaporation increases by using the SLHX. Whereas one of
the disadvantages of the SLHX is the suction gas density drop due to the suction
gas superheating, the SLHX contributes to a lower volumetric capacity. However,
these two opposing effects resulted in a lower compressor speed with the same
refrigerant mass fractions and capacity.

When the performance of R32/R152a with SLHX is compared with that of

R32/R134a, the R32/R134a mixtures performed better in the cooling mode above
35% of R32 mass fraction. Essentially, both mixtures with SLHX below 30% R32
mass fraction performed similarly.
5.1.2.3 Conclusion
• For R32/R152a mixtures, the mass fraction of R32 should be higher than
40% to ensure a heating capacity comparable to R22 capacity for all
operating conditions.
• R32/R152a mixtures showed a significant increase in COP (14 to 20%)
for cooling conditions with a counterflow heat exchange configuration.
• R32/R152a mixtures have the lowest GWP possible of the tested mixtures,
about one fourth of the R22 value, and are flammable in the whole mass
fraction range.
• R32/R134a mixtures showed better or equivalent performance than
R32/R152a when the mass fraction of R32 was higher than 35%. Specif-
ically, the heating performance of R32/R134a mixtures is better than that
of R32/R152a due to its larger volumetric capacity at the same R32 mass
fraction.
• R32/R134a mixtures are “controllable-flammable” mixtures since they are
the mixture of flammable R32 and nonflammable R134a.
• The potential benefits of SLHX are a higher performance for the given
R32 mass fraction. Therefore, the R32 mass fraction can be lowered until
the same volumetric capacity is obtained. This reduces the flammability
of R32 rich mixtures. In fact, the COP increases for both mixtures over
R22 up to 20% when the mass fraction of R32 was 40% and counterflow
heat exchanger is used.
• R32/R134a mixtures with SLHX showed a higher COP increase over the
case without SLHX than did R32/R152a mixtures.
• R32/R134a and R32/R152a are potential alternatives for R22 since both
mixtures showed a comparable performance if the appropriate mass frac-
tion mixture is chosen and counterflow heat exchange with the heat transfer
fluid is possible.
5.1.3 ORNL BREADBOARD HEAT PUMP

The following text is based on excerpts of the earlier mentioned papers. The full
texts are available from Vineyard, 1988; Vineyard and Conklin, 1991; Conklin and
Vineyard, 1991; and Vineyard, Conklin, and Brown, 1993.

ORNL’s breadboard heat pump is very similar to that of NIST’s breadboard heat
pump I, shown in Figure 5.1.1, except no evaporator calorimeter enclosure is used
in ORNL’s setup. ORNL’s breadboard used water as the heat source- and sink-fluid
and coaxial tube-in-tube counterflow heat exchangers for both heat exchangers.

TABLE 5.3
Test Conditions
Variable Cooling Mode Heating Mode
Evaporator inlet water temperature [°C] 26.7 5.6/15.6

Condenser inlet water temperature [°C] 29.4/38.9 15.6
Evaporator-side water temperature difference [°C] 20 5.6
Condenser-side water temperature difference [°C] 20 11.1
Source: Vineyard, 1988.
5.1.3.2 R13B1/R152a Test
Vineyard (1988) experimentally investigated the effects of R13B1 mass fraction of

R13B1/R152a mixture on capacity control. Vineyard chose the R13B1/R152a mix-
ture for his study because the boiling points of the pure components are moderate
(not exceeding 16.7°C), recommended by Radermacher (1986) as a temperature
glide for the heat pump application efficiency not to deteriorate. The R13B1 mass
fraction of R13B1/R152a mixtures was varied at 25, 50 and 75% for cooling and
heating test conditions as specified in Table 5.3. Both heat exchangers had the same
geometry: refrigerant tube outside diameter, 25 mm; water tube outside diameter,
14 mm; and total tube length, 3 m. Results of cooling and heating tests are summa-
rized in Figure 5.1.22. As shown in Figure 5.1.22(a), the cooling capacity of pure
R152a was 28% lower than that of R22. Therefore, decreasing the mass fraction of
R13B1 for the lower ambient temperature cooling could reduce the cycling loss.
Increasing the mass fraction of R13B1 could increase the heating capacity at
the lower ambient temperature heating. As shown in Figure 5.1.22(b), the heating
capacity of pure R152a was 33% lower than that of R22.
Moreover, the cooling and heating COPs both increased as the mass fraction of
R152a increased, as shown in Table 5.4. The COP comparison tests were conducted
while maintaining equivalent inlet and outlet water temperatures in the evaporator
and condenser for both R22 and the mixtures. In conclusion, Vineyard experimentally
confirmed that the cooling and heating capacity could be modulated by 25 to 28%
by the mass fraction shift. Moreover, the estimated annual energy consumption
savings was approximately 7 to 12% by decreasing the cycling losses.
5.1.3.3 R143a/R124 Test
Vineyard and Conklin (1991) experimentally investigated the effects of heat

exchanger surfaces on the performance of zeotropic mixture R143a/R124 (75/25
wt.%) to improve refrigerant side heat transfer coefficients. In their study, three
enhanced tubes — fluted, finned and microfin — were compared to the smooth tube.
Detailed geometry of theses tubes is summarized in Figure 5.1.23 and Table 5.5.
Test conditions used were based on DOE cooling conditions (27.8˚C). Reference
pressures were 700 kPa (12˚C saturation temperature) for the evaporator and 1700 kPa

Outdoor temperature (°C)
Outdoor temperature (°C)
−17.8 −6.7 4.4 15.8
23.9 29.4 35.0 40.6 20 5.9
16 4.7
16 Resistance 4.7
Cooling Capacity (KBtu/h)
Cooling Capacity (kW)
Heating Capacity (KBtu/h)

3.5 heat savings
Heating Capacity (kW)

12
Cycling savings
R22
12 R1381 3.5
50% R1381 75% R1381 Cycling
8 25% R1381 2.3 R22 savings
R152a 50% R1381
8 R152a 2.3
Building load 25% R1381
4 1.2 Building load
4 1.2
0 0
0 0
(a)
1.0
4.0
R152a
R152a
Measured COP
25% R1381 R22
Measured COP
2.5 25% R1381
R22 3.6
50% R1381 50% R1381
75% R1381
2.0 3.0
R1381 C
1.5 2.5
75 85 95 105 0 20 40 60
Outdoor temperature (°F) (b) Outdoor temperature (°F)
FIGURE 5.1.22 Cooling performance of R13B1/R152a (Vineyard, 1988). (a) Cooling. (b) Heating.

TABLE 5.4
Test Results
R13B1/R152a R13B1/R152a R13B1/R152a
Refrigerant R22 R152a (25/75 wt.%) (50/50 wt.%) (75/25 wt.%)
Cooling COP 2.4 2.7 2.5 2.3 —

Heating COP 3.7 3.7 3.6 3.5 3.3
Source: Vineyard, 1988.
P
e
do di
(a) Fluted Surface
47° do di
f
(b) Finned Surface
23°
do di
f
(c) Microfin Surface
FIGURE 5.1.23 Three enhanced surface tubes (Vineyard and Conklin, 1991).
TABLE 5.5
Geometry of Enhanced Tubes
Smooth
Tube Type Tube Fluted Tube Finned Tube Microfin Tube
Outside diameter [mm] 15.8 18.9 15.8 14.8

Thickness [mm] 1.0 1.1 1.1 0.5
Other [mm] — Spiral indentation: 0.8 Fin height: 0.432 Fin height: 0.305
Pitch: 12.7
Heat exchanger length 2.75/1.94 2.39/1.94 2.39/1.94 2.39/1.94
(evaporator/condenser)
[m]
Source: Vineyard and Conklin, 1991.

7
27.8°C DOE Rating
Condition
6 R22-Dotted Lines
Coefficient of performance (COP)
Finned, Fluted 75% R143/25% R124

-Solid lines
5
Fluted Finned, Micro-Fin
4
Smooth
3
???
NO. ANGLE
Finned 0.432 10 47°
2
Micro-Fin 0.305 75 23°
1
5 6 7 8 9 10 11 12 13 14
Capacity (kW/h)
FIGURE 5.1.24 Cooling performance of R143a/R124 (Vineyard and Conklin, 1991).
(45˚C saturation temperature) for the condenser. Evaporator inlet quality was approx-
imately 0.25 and the degree of the superheating at the evaporator outlet was approx-
imately 3 to 5˚C.
Test results of R22 and R143a/R124 with the smooth tube and three enhanced
tubes are shown in Figure 5.1.24 and summarized as follows:
• Enhanced surface tubes significantly improved the COPs of both R22 and
R143a/R124. COP improvement of R143a/R124 was larger than that of R22.
• When the capacity exceeded approximately 7 kW, the COP of R143a/R124
dropped rapidly due to the greater pressure drop and refrigerant side heat
transfer degradation associated with zeotropic mixtures.
• Different enhanced tubes worked better for the evaporator and condenser.
Using a fluted tube for the evaporator and a finned tube for the condenser
resulted in the best performance improvement (11 to 23%) over R22.
5.1.3.4 R143a/R124 and R32/R124 Test
As a continuing effort from Vineyard and Conklin (1991) to improve system COP,
Vineyard et al. (1993) experimentally investigated three methods of improving heat
transfer enhancements, inserts, finned tube and a segmented evaporator.
Inserts
Perforated foil inserts were used inside of the inner tube. The perforated brass foil
(w = 0.23 mm, t = 0.05 mm, 50 holes/cm2) was used for the second through fourth
evaporator passes to enhance the nucleate boiling for the low quality region. The
aluminum bent tabs, shown in Figure 5.1.25, were inserted in the second through
seventh condenser passes.

30°
t
FIGURE 5.1.25 Geometry of bent-tab insert (w = 13.33 mm, t = 0.8 mm, = 2.75 m long)
(Vineyard et al., 1993).
Annulus Wall
Water Flow
47° do di
Refrigerant
Flow f
Water Flow
FIGURE 5.1.26 Geometry of finned tube (do = 15.8 mm, di = 13.7 mm, f = 0.38 mm)
(Vineyard et al., 1993).
Finned Tube
A commercially available finned tube was used for the refrigerant side tube, as
shown in Figure 5.1.26.
Segmented Evaporator
The segmented evaporator was designed to enhance the nucleate boiling heat transfer
for the low vapor quality region and the convective boiling heat transfer for the high
vapor quality region. Evaporator passes 1 through 4 used a rolled-fin surface as
shown in Figure 5.1.27 and evaporator passes 5 through 8 used a finned tube surface
as shown in Figure 5.1.26. Two sections then formed the segmented evaporator, as
shown in Figure 5.1.28.
Test results of four tube combinations for the evaporator and condenser are
shown in Figure 5.1.29. As shown in (a), the bent-tab inserts and the finned tube
cases were compared to the smooth tube case for R22 and R143a/R125. The smooth-
tube performance of R143a/R125 was 13 to 27% lower than that of R22. The first

Annulus Wall
Refrigerant Flow
Reentrant
Cavity
Surface
Tube
Wall
Water Flow
LC
FIGURE 5.1.27 Rolled-fin tube (Vineyard et al., 1993).
set of tube enhancements for R143a/R125, the perforated foil evaporator and bent-tab
condenser, showed no COP improvement due to the high pressure drop. The second
set of tube enhancements for the R143a/R125, the perforated foil evaporator and
finned tube condenser, showed a 15% COP improvement over the R22 at the lowest
capacity and 6% lower COP than that of R22 at the highest capacity. This COP
decrease for the higher capacity was due to the increased pressure drop at the higher
refrigerant mass flow rate. The third set of the combination was the segmented
evaporator and finned condenser. For the third set, R143a/R124 showed a 5 to 9%
COP improvement over R22 and R32/R124 showed a 9 to 17% COP improvement
over R22. When the third set was compared to the smooth tube case, R22 showed
a 22 to 27% improvement and R143a/R124 showed a 62 to 80% improvement.
In summary, the following conclusions were obtained.
• The inserts were ineffective to improve the COP of zeotropic mixtures,

R143a/R124 and R32/R124.
• Using the surface enhancement, especially the segmented evaporator and
finned condenser pair, improved the COP of zeotropic mixtures relative
to R22.
• R32/R124 showed almost twice better performance than R143a/R124.

Refrigerant in
T/C
Water Out Pressure
RTD Transducer H20 T/C
REF T/C
REF T/C H20 T/C
REF T/C
Water
REF T/C Refrigerant

Pressure
Transducer
REF T/C
REF T/C H20 T/C
REF T/C
H20 T/C
Refrigerant Out
T/C
Pressure RTD
Transducer Water in
FIGURE 5.1.28 Segmented evaporator (Vineyard et al., 1993).
5.2 ACTUAL SYSTEM TESTS EXPERIENCE

This section describes experimental investigations for the performance of refrigerant
mixtures in actual systems conducted at CEEE (Hwang et al., 1995) and NIST
(Mulroy and Didion, 1986; Rothfleisch and Didion, 1993).
5.2.1 HEAT PUMP TEST AT CEEE

A test facility called a psychrometric calorimeter was set up to measure the steady
state performance of an air-to-air heat pump. The test facility consisted of a closed
indoor loop, an environmental chamber and a data acquisition system. The closed indoor
loop was equipped with devices that measured the dry bulb and dew point temper-
atures of the air and a nozzle that measured the air flow rate downstream of the test
unit, as shown in Figure 5.2.1. The test chamber was equipped with an air handling
unit, as shown in Figure 5.2.2, so it could simulate the summer and winter climate
conditions defined by ASHRAE Standard 116, Table 5.6 (ASHRAE, 1995).

Capacity (1000 W)
Capacity (1000 W)
5 7 9 11 13
5 7 9 11 13 7
7
Segmented, Finned
6
6
Coefficient of Performance (COP)

Coefficient of Performance (COP)
Foil, Finned 5
5
4 4
Smooth Foil, Bent Tab Smooth

3 3
82°F(27.8°C) DOE Rating Condition

82 °F(27.8°C) DOE Rating Condition 2 HCFC-22-Solid Lines
2
HCFC-22-Solid Lines 75% HFC-143a/25% HCFC-124-Dashed Lines
75% HFC-143a/25% HCFC-124-Dashed Lines 30% HFC-32/70% HCFC-124-Dashed Lines
1 1
12 16 20 24 28 32 36 40 44 48 12 16 20 24 28 32 36 40 44 48
Capacity (1000 Btu/h) Capacity (1000 Btu/h)
(a) (b)
FIGURE 5.1.29 Cooling performance enhancement (Vineyard et al., 1993).

AIR
HANDLER
FLOW
Temperature grid
with 9 thermocouples Blower
Pressure Taps
m T PT
Discharge
T Chamber
Ref. in Exp.Valve Wet- and dry-bulb
T
Coil T temperature
PT Diffusion
Ref. out T Baffle
T
Manometer T
INDOOR
Condensed
Water out TEST Wet- and dry-bulb
temperature
Diffusion Receiving
UNIT Manometer Baffle Chamber
Manometer
Pressure Two air stream mixers

Taps Temperature grid
with 9 thermocouples
FIGURE 5.2.1 Closed indoor loop (Hwang et al., 1995).

FLOW
AIR HANDLER
OUTDOOR TEST UNIT
T with 5
thermocouples Wet-and dry-bulb
Extended temperature
Duct
Ref. out
P T
Coil
P T
FLOW
Code for outdoor unit:
T T Temperature grid unit is shown during cooling mode
Compressor T : Temperature measurement
with 9 thermocouples P : Pressure measurement
Ref. in
FIGURE 5.2.2 Outdoor chamber (Hwang et al., 1995).

TABLE 5.6
ASHRAE Test Conditions
Indoor Indoor Outdoor Outdoor
Dry Bulb Wet Bulb Dry Bulb Wet Bulb
Test (˚C) (˚C) (˚C) (˚C)
A 26.7 19.4 35.0 23.9

B 26.7 19.4 27.8 18.3
C 26.7 <13.9 27.8 18.3
D 26.7 <13.9 27.8 18.3
High temperature (47S) 21.1 15.6 8.3 6.1
Cyclic (47C) 21.1 15.6 8.3 6.1
Frost accumulation (35F) 21.1 15.6 1.7 –1.1
Low temperature (17L) 21.1 15.6 –8.3 –9.4
Source: ASHRAE, 1995.
5.2.1.2 Test Unit
The test unit was a 7.0 kW capacity split heat pump system using a reciprocating
compressor and two expansion devices. One expansion device was a thermostatic
expansion valve (TEV) for the heating mode and the other was a short tube restrictor
(ST) for the cooling mode. Figure 5.2.3 shows the heat exchange configuration for
the indoor coil. The indoor unit was installed at an inclination of 20˚ from the vertical
with downward airflow, as shown in Figure 5.2.3. The test unit was designed for
Heating Air Flow
Refrigerant Flow
Cooling
Heating
Cooling
FIGURE 5.2.3 Indoor-side heat exchanger (Hwang et al., 1995).

R22; therefore, the original components were used for the evaluation of the refrig-
erants having a similar vapor pressure with R22. Except for the ST, the R22 tests
were carried out without making any modifications to the system while the mixture
tests were carried out after changing the lubricant for the compressor from mineral
oil to ester oil and changing the filter drier. When testing higher vapor pressure
refrigerants than R22, the compressor and TEV designed for higher operating pres-
sures were used. As compared to the original compressor, calorimeter tests performed
by the compressor manufacturer showed that the high pressure compressor had 4%
lower efficiency at 54.4˚C condensing temperature and 7% higher efficiency at
37.8˚C condensing temperature.
5.2.1.3 Refrigerants Investigated
Several hydrofluorocarbon (HFC) refrigerants have been proposed by refrigerant

manufacturers to replace R22, frequently used as a refrigerant in air-conditioning
and heat pump systems. In this study, three replacements were investigated: a ternary
mixture of R32/R125/R134a in the mass fraction of 23/25/52 wt.% (R407C) and
two binary mixtures, R32/R125 in the mass fraction of 50/50 wt.% (R410A) and
R32/R125 in the mass fraction of 45/55 wt.% (R410B). These refrigerants are non-
ozone-depleting substances, as shown in Table 5.7. With the exception of the tem-
perature glide, R407C has similar thermodynamic properties to those of R22, as
shown in Table 5.8. Therefore, similar size hardware, such as the compressor and
the heat exchangers, can be utilized. The vapor pressure curve of R407C is close to
that of R22, as shown in Figure 5.2.4, but it is slightly higher at higher temperatures
and slightly lower at lower temperatures than that of R22.
The pressure ratio tends to be higher than that of R22 when R407C has similar
evaporating and condensing temperatures to those of R22, defined as the average
temperatures of saturated liquid and saturated vapor. As seen in Table 5.5, R407C is
the only refrigerant studied here that has a significant temperature glide, so the heat
exchange geometry can have a significant effect on the performance of this refrigerant.
The two binary mixtures have a higher latent heat and heat capacity than those
of R22 and these benefits can lead to higher capacities. The saturated vapor density
TABLE 5.7
Environmental and Safety Properties of Refrigerants Investigated
Refrigerant R22 R407C R410A R410B
Components HCFC-22 HFC-32/125/134a HFC-32/125 HFC-32/125

(23/25/52 wt.%) (50/50 wt.%) (45/55 wt.%)
O.D.P. (CFC-11=1.0) 0.055a 0a 0b 0c
G.W.P. (CO2 = 1.0) 1600a 1600a 2200b 2020c
Flammability No No No No
a DuPont, 1994; b Allied Signal Chemicals, 1995; c DuPont, 1995.
Source: Hwang et al., 1995.

TABLE 5.8
Thermodynamic Properties of Refrigerants Investigated
(Hwang et al., 1995)
Molecular weight [g/mol] 86.5 86.21a 72.62b 75.63c

Normal boiling point [˚C] –40.9 –43.61a –52.72b –51.83c
Critical temperature [˚C] 96.2 86.71a 72.52b 71.63c
Critical pressure [bar] 50.5 46.21a 49.52b 47.83c
Latent heat at 25˚C [kJ/kg] 180.6 189.3 194.0 184.9
Bubble pressure at 25˚C [bar] 10.4 11.9 16.5 16.4
Liquid density at 25˚C [kg/m3] 1192 1154 1083 1096
Saturated vapor density at 25˚C [kg/m3] 44.5 42.5 62.2 64.5
Temperature glide at 1 atm [K] 0.0 7.1 0.1 0.1
Sat. liquid heat capacity at 10˚C [kJ/kg K] 1.23 1.41 1.48 1.46
Sat. liquid heat capacity at 50˚C [kJ/kg K] 1.47 1.68 1.92 1.89
Sat. vapor heat capacity at 10˚C [kJ/kg K] 0.81 0.88 0.94 0.94
Sat. vapor heat capacity at 50˚C [kJ/kg K] 1.17 1.20 1.54 1.55
a DuPont, 1994; bAllied Signal Chemicals, 1995; c DuPont, 1995.
Source: Gallagher et al., 1993, unless otherwise noted. Hwang et al., 1995.
10
3
Vapor Pressure [MPa]
0.5
0.3 R-22
R407C
0.2 R410A
R410B
0.1
−20 −10 0 10 20 30 40 50 60 70
Temperature [°C]
FIGURE 5.2.4 Vapor pressures.

of these refrigerants is approximately 44% higher than that of R22, which also
translates into higher capacities for the same size compressor. To test the fluids with
the original heat exchangers, the displacement of the compressor had to be reduced
to a similar capacity. These binary mixtures have a higher vapor pressure by approx-
imately 60% compared to R22 but the slope of the vapor pressure curve is quite
similar to that of R22 in the temperature range of interest (Figure 5.2.4). Therefore,
the pressure ratio of these refrigerants is expected to be similar to that of R22.
5.2.1.4 Test Procedure
Capacity Measurement
The experiments to measure the capacity and COP were performed based on
ASHRAE Standard 116 (ASHRAE, 1995) and ARI Standard 210/240 (ARI, 1994).
In this study, the air side capacity and the refrigerant side capacity were measured.
The loop air enthalpy method was used to measure the air side capacity: the air flow
rate and air enthalpy difference between inlet and outlet of the indoor coil were
measured. A nozzle apparatus measured the air flow rate. In measuring the refrigerant
side capacity, the refrigerant mass flow rate and the refrigerant enthalpies at the inlet
and outlet of the heat exchanger were used. The mass flow rate was measured by a
Coriolis-type mass flowmeter and the refrigerant enthalpies were calculated by
REFPROP Version 4.0 (Gallagher et al., 1993) from the temperature and pressure
measurements.
ASHRAE Standard 116 (1995) requires that the capacities determined using
these two methods agree within 6% of each other. The two methods agreed within
3% for all tests conducted in this study. The reported capacity and COP values were
based on air side values. The refrigerant side values were used only to check the
total energy balance and to prove the validity of the test.
Test Procedures
The experimental tests were carried out with refrigerants R22 and its alternatives,
R407C, R410A and R410B. First, the R22 “baseline” test and the “retrofit” test for
R407C were performed. The baseline R22 tests were conducted without making any
modifications to the system. In the retrofit tests, only the refrigerant charge was
optimized to find the optimum charge that gave the maximum COP at ASHRAE
cooling test A condition. After the optimum charge was found, ASHRAE tests were
carried out to compare the performance of each refrigerant and mixture.
Second, the “soft optimization” was carried out for all refrigerants tested to
maximize both the cooling and heating COP. The combination of the expansion
devices and the refrigerant charge was chosen to maximize both the cooling COP
for ASHRAE cooling test B and the heating COP for ASHRAE heating test 47S.
At first, the optimum charge for heating was obtained by adjusting the refrigerant
charge at the 47S heating test conditions. The optimum charge was chosen such that
the maximum COP could be obtained. To find the ST for the cooling mode that
corresponds with the optimum charge in the heating mode, several charge optimi-
zation tests were run with different size STs at the cooling test conditions.

7.6 3.15
3.10
7.4
Cooling Capacity [kW] 3.05
3.00
COP
7.2
2.95
R-22 COP
2.90
7.0
R-407C Capacity
2.85
R-22 Capacity R-407C COP
6.8 2.80
3.6 3.9 4.1 4.3 4.5
Charge [kg]
FIGURE 5.2.5 Charge optimization of R22 and R407C (Hwang et al., 1995).
5.2.1.5 Test Results
R22 Baseline Test

The charge optimization test results for R22 are shown in Figure 5.2.5. When
increasing the charge, the capacity and COP for R22 increase to a maximum point
and then decrease. COP for R22 reaches a maximum at approximately 4.0 kg charge
and the capacity reaches a maximum at 4.2 kg charge. By increasing the charge, the
amount of subcooling increases while the superheat decreases. Throughout the
ASHRAE tests, the refrigerant charge was maintained at 4.0 kg, corresponding to
the maximum COP for ASHRAE Cooling Test A.
R407C Retrofit Test
The mixture R407C was first tested as a “retrofit.” Only the refrigerant charge was
optimized to obtain maximum COP. The same procedure used for R22 was used for
the charge optimization test of R407C and the results are shown in Figure 5.2.5.
The COP is at maximum at approximately 4.0 kg, the same as that of R22. After
these tests, ASHRAE tests were carried out with the optimum charge. The results
for both R22 and R407C are listed in Tables 5.9 and 5.10.
Comparison of R22 Baseline, R407C Retrofit
The retrofit test results for R407C are compared with R22 baseline test results in
Table 5.9 for cooling test A and heating test 47S. In Table 5.10, the test results for
ASHRAE cooling test B and heating test 17L are compared. The retrofit test results
for R407C show a 2.6% higher capacity and a 4.5% lower COP in the cooling test
A case and a 6.4% lower capacity and a 16.5% lower COP in the heating test 47S
case as compared to the R22 baseline (Table 5.9). Cooling test B has similar results
to cooling test A case (Table 5.10) while heating test 17L has a greater degradation
than the heating test 47S case (Table 5.10). Although R407C has similar thermo-
dynamic characteristics as R22, some key cycle parameters are different. R407C
shows a 16.5% higher pressure ratio compared to that of R22 for the cooling A case.

TABLE 5.9
Comparison of ASHRAE Cooling A and Heating 47S Test Results
Test Type R22 Baseline R407C Retrofit
Test Mode Cooling A Heating 47S Cooling A Heating 47S
Capacity [kW] 6.95 6.24 7.13 5.84

COP 3.08 3.03 2.94 2.53
Tdischarge [˚C] 85.5 83.2 82.0 96.5
Tsuction [˚C] 22.6 8.7 21.8 9.9
Pcond [kPa] 1768.7 1793.9 2124.2 2678.9
Pevap [kPa] 712.7 507.4 736.2 502.9
Pressure ratio 2.48 3.54 2.89 5.33
Subcooling [K] 9.6 21.1 14.0 39.9
Superheating [K] 11.1 9.9 11.3 11.3
TABLE 5.10
Comparison of ASHRAE Cooling B and Heating 17L Test Results
Test Type R22 Baseline R407C Retrofit
Test Mode Cooling B Heating 17L Cooling B Heating 17L
Capacity [kW] 7.12 3.40 7.13 2.69

COP 3.52 2.09 3.22 1.59
Also, the cycle shifts to higher evaporating and condensing pressures. The higher
pressure ratio lowers the compressor efficiency. Although R407C has a slightly
higher capacity; it has a lower COP.
R407C retrofit shows more degradation for heating than for cooling. This can
be explained by the heat exchange configuration of the indoor coil as shown in
Figure 5.2.3. The heat exchanger configuration contributes to the capacity degrada-
tion in the heating mode, especially for mixtures that have a temperature glide.
Soft Optimization Test Results
To improve the steady-state performance of the mixture, the soft optimization was
carried out for R22, R407C, R410A and R410B that could reconcile the imbalance
between the cooling and heating optima. As already mentioned, the optimum charge
was found for the heating test 47S, then the ST was adjusted so that the optimum-
cooling COP occurs at the same charge. When the optimum charge was the same
for different sizes of STs as for R410B, the subcooling and superheating were
evaluated to choose the optimum ST size. For R410B, a 1.55 mm ST has the wider
range of refrigerant charge with acceptable subcooling and superheating than those
of 1.60 mm ST. Therefore, the 1.55 mm ST was chosen for R410B and the result

TABLE 5.11
Optimum Charge for Each Operating Mode
Heating optimum charge [kg] 3.6 3.4 3.6 3.4

Cooling optimum charge [kg] 3.6 3.4 3.6 3.8
ST size [mm] 1.65 1.70 1.55 1.55
of this procedure is shown in Table 5.11. Except for R410B, it was possible to adjust
the charge and ST so the optimum charges for heating and cooling test conditions
were the same. For R410B, the average between the optimum heating and cooling
charges was used. The larger ST, 1.65 mm, was also tested but the reasonable values
of subcooling and superheating were not obtained. This mismatch could have been
eliminated or minimized if the more finite increases for the size of STs and refrigerant
charges were tested.
Steady State Performance Results
After the soft optimization tests, ASHRAE tests were carried out with the optimum
refrigerant charge and ST. Test results for capacity and COP are compared with
other data in Tables 5.12, 5.13 and 5.14. R407C had approximately the same cooling
and heating capacity (within 3% of R22) but also a slight degradation in cooling
and heating COP (4 to 8%). The existing heat exchanger was not suited for utilizing
the temperature glide of this mixture and contributed to the slight degradation in
capacity. As expected, this refrigerant had a larger pressure ratio and this also might
contribute to the degradation in COP.
The two binary mixtures showed higher cooling capacity by up to 7% and COP
up to 4% compared to those of R22 despite the smaller compressor. These refrig-
erants also had better heating capacity by 3 to 6% at 47S and up to 20% in the 17L
TABLE 5.12
ASHRAE Cooling A Test Results
Capacity [kW] 6.82 6.89 7.16 7.07

COP 3.20 3.06 3.25 3.23
Tdis [˚C] 76.3 78.1 75.7 75.0
Tsuc [˚C] 18.0 23.3 20.5 20.8
Pcond [kPa] 1641.8 1825.9 2611.8 2587.3
Pevap [kPa] 707.5 704.6 1097.1 1081.1
Pressure ratio 2.32 2.59 2.38 2.39
Subcooling [K] 4.0 4.8 2.8 3.7
Superheating [K] 6.7 14.3 10.0 10.6

TABLE 5.13
ASHRAE Heating 47S Test Results
Capacity [kW] 6.13 5.95 6.51 6.29

COP 3.13 2.96 3.02 3.03
Tdis [˚C] 81.4 77.1 71.6 65.5
Tsuc [˚C] 9.2 8.9 2.0 2.1
Pcond [kPa] 1678.5 1860.3 2618.0 2435.1
Pevap [kPa] 494.6 478.9 826.3 812.8
Pressure ratio 3.39 3.88 3.17 3.00
Subcooling [K] 20.2 21.4 17.1 10.5
Superheating [K] 9.5 11.7 0.8 1.2
TABLE 5.14
ASHRAE Cooling B and Heating 17L Test Results
B capacity [kW] 7.34 7.16 7.83 7.64

B COP 3.78 3.49 3.92 3.88
17L capacity [kW] 2.77 2.75 3.32 3.33
17L COP 1.97 1.82 1.87 1.89
test. R410A and R410B showed similar cooling and heating performances when
compared with each other.
As expected, these refrigerants have higher evaporating and condensing pres-
sures by approximately 60% compared with those of R22 and the pressure ratio was
nearly the same as that for R22.
The results of this study for R407C and R410B are compared with the results
presented by AREP (Alternative Refrigerants Evaluation Program) (Godwin, 1993)
in Table 5.15, while the results of R410B are compared with the results by Kol-
liopoulos (1994). Overall, the data of this study agree well with the AREP data. For
R410B, the data show good agreement with those of Kolliopoulos except for the
low temperature heating capacity, which is higher than that of Kolliopoulos. This
significant gain in capacity arises because at higher ambient temperatures and there-
fore higher capacities, the heat exchangers are slightly undersized for the high
pressure fluids. This occurs because it was not possible to exactly match the high
pressure compressor’s capacity to that of the existing system. Support for this
conclusion comes from the minimal superheating.
For the data presented here, the TEV maintained the superheating as low as 1
to 2˚C while in the Kolliopoulos data, the superheating was maintained at 11.1˚C.

TABLE 5.15
Comparison of Results with AREP Data
Cooling Cooling Heating Heating
Refrigerant Source Capacity COP Capacity COP
R407C Present study 0.98–1.01 0.92–0.96 0.97–0.99 0.92–0.95

AREP 0.93–1.01 0.90–0.97 0.98–1.02 0.93–1.02
R410A Present study 1.05–1.07 1.02–1.04 1.06–1.20 0.95–0.97
AREP 0.98–1.05 1.01–1.06
R410B Present study 1.04 1.01–1.03 1.03–1.20 0.96–0.97
Kolliopoulos, 1994 0.99–1.00 0.98–1.00 0.99–1.03 1.03–1.09
Note: The above data are the ratios of each refrigerant performance to R22 performance.
Another difference is that a reciprocating compressor was used in this study and a
scroll compressor was used in the Kolliopoulos study.
Seasonal Performance Results
When evaluating the overall performance of heat pumps, including the steady state
and cyclic performances, the seasonal performance factors seasonal energy efficiency
ratio (SEER) and heating seasonal performance factor (HSPF) are used. These factors
are important because they approximate operation over an entire season. The sea-
sonal performance was calculated based on ASHRAE Standard 116 (ASHRAE,
1995). Eight different ASHRAE test results, including the steady state and cyclic
performances, were used in this calculation.
The seasonal performance factors for each refrigerant are calculated and com-
pared in Table 5.16. Relative to R22, R407C has a 6.8% lower SEER and a 4.7%
lower HSPF, while R410A has a 2.6% higher SEER and nearly the same HSPF and
R410B has a 1.7% higher SEER and a 1.8% higher HSPF. Two binary mixtures
have lower COP for 47S test conditions but their better cyclic performance contrib-
utes to having a slightly better HSPF.
R407C, having similar operating pressures as R22, has the advantage of being
a retrofit, which means minimal changes to the system for a quick switch to alter-
natives. Only the expansion devices and the refrigerant charge must be chosen
carefully to have performance within 7.8% of R22. R407C has a 6.8% lower cooling
seasonal performance and a 4.7% lower heating seasonal performance as compared
to R22. The reduction in performance as compared to R22 is relatively small and
can be overcome with systems specifically designed for R407C.
The two binary refrigerants require careful design considerations, especially heat
exchangers, pipes and compressors, due to the much higher operating pressures.
Although these binary refrigerants need significant system modification, they have
the benefit of higher steady state and seasonal performances. These benefits could
be even greater if the system is designed specifically for these fluids. Overall, the
binary fluids perform better than R22. R410A has a cooling seasonal performance

TABLE 5.16
Seasonal Performance Test Results
SEER [Btu/kW-hr] 11.7 10.9 12.0 11.9

HSPF 1.70 1.62 1.70 1.73
Notes:
1. Conditions in SEER calculation.
(a) Oversize factor: 10%.
(b) Design temperature of 35˚C (needs eight temperature
bins ranging from 18 to 41˚C).
(c) The bin hours are based on the U.S. national average
climate.
(d) The building load (BL) was selected from the R22
baseline case.
2. Conditions in HSPF calculation.
(a) The regional outdoor temperature: –22˚C.
(b) Location requires 18 temperature bins ranging from –32
to 18˚C.
(c) The bin hours were based on Region V in ARI Standard
210/240 (1994).
that is 2.6% better than R22 and a heating seasonal performance that is essentially
the same as R22. R410B has cooling and heating seasonal performances that are
1.7 and 1.8% better than R22, respectively.
5.2.1.6 Effects of Heat Exchanger Geometry

on Mixture Performance
As explained in Section 3.8, the temperature glide of zeotropic mixtures can be
utilized in counter flow heat exchange. Counter flow heat exchange can reduce the
average temperature difference between the two heat exchanging streams so the
cycle can approach a Lorenz cycle, resulting in reduction of the thermodynamic
external irreversibility and consequently having a higher heat exchange efficiency.
It is very important to achieve the counter flow heat exchange configuration for the
heat exchanger when using zeotropic mixtures.
Path Modification Test (R407C only)
To implement the benefit of a temperature glide of the zeotropic mixture refrigerant
R407C, the path modification option was examined. The path modification requires
altering the refrigerant path to attain a near counter flow configuration in the indoor
coil for the heating mode. The indoor coil of the test unit has a quasi-cross flow
heat exchange configuration. In the cooling mode, the refrigerant flows from bottom
to top, whereas in the heating mode the refrigerant flows from top to bottom, as

shown in Figure 5.2.3. The heat exchange pattern between air and refrigerant is near
counter flow for the cooling mode but it is near parallel flow for heating. Installing
four check valves, as shown in Figure 5.2.6, changed the indoor coil path to supply
the refrigerant to the indoor coil in the same direction regardless of the action of
the four-way valve. With this path modification, the refrigerant could be supplied
into the indoor coil from bottom to top for both cooling and heating modes to
maintain a near counter flow heat exchange between air and refrigerant at all times.
This option is important when using zeotropic mixtures that have a temperature
glide because the refrigerant path is reversed depending on the operating mode in
a heat pump.
Path modification results show a 3.7% lower capacity and a 5.5% lower COP
for cooling test A as compared to that of R22, as shown in Table 5.17. The four
additional check valves cause an additional pressure drop, resulting in a lower mass
flow rate and a lower evaporating pressure. But it shows a significant improvement
in the heating COP (10.3%) for heating test 47S, as compared to the retrofit case
shown in Table 5.18. The greatest improvement for path modification can be
observed in the low temperature heating test 17L: 15.6% for capacity and 17.6%
for COP, as shown in Table 5.19.
The refrigerant temperatures along the cycle for retrofit and path modification
are compared in Figures 5.2.7 and 5.2.8 for cooling test A and heating test 47S. In
these figures, the x-axis is not to scale; it indicates just the sequence of each
temperature probe as the refrigerant passes on its way through the cycle. The first
point is the compressor discharge and the last point is the compressor inlet. The
profile for the cooling of R407C is similar to that of R22. The heating case shows
a higher compressor discharge temperature and a lower evaporating temperature than
that of R22, resulting in a high pressure ratio for R407C. The temperature profiles
in the evaporator and condenser show large differences. These temperature profiles
explain the performance degradation of the retrofit case, which had the large tem-
perature difference because of the near parallel flow configuration. They also explain
the performance improvement due to path modification, which resulted in a small
temperature difference because of the near counter flow configuration. The path
modification can improve the performance by reducing the thermodynamic irrevers-
ibility. Although path modification improved the performance of the R407C over
the retrofit, it still experiences degradation as compared to R22, especially in the
heating mode: a 4.2% lower capacity and a 7.9% lower COP at heating test 47S.
The reason for this degradation is the retrofit was performed after the charge was
optimized at cooling test A conditions without optimization at the heating test
conditions, so degradation of the heating performance is natural. These results
indicate that more extensive optimization is necessary, such as the soft optimization.
5.2.2 HEAT PUMP TEST AT NIST

Manufacturers must take care of existing products in the field and products to be
shipped until new systems replace them. Therefore, an implementation of short-term
alternatives is as important as the long-term alternatives. “Retrofit” (or drop-in)
refrigerants are short-term alternatives since they only require minor system changes.

Air Flow Ball Valve
Switch
Over Valve
Indoor Check Valve
Coil
Comp Outdoor
Coil
Short Tube
Thermostatic
FLOW DIRECTION Expansion
Cooling Valve
Heating
Path Modification Heating
Check Valve
FIGURE 5.2.6 Schematic cycle diagram of path modification (Hwang et al., 1995).

TABLE 5.17
Comparison of ASHRAE Cooling A Test Results
Case R22 Base R407C Retrofit R407C Path Modification
Capacity [kW] 6.95 7.13 6.69

COP 3.08 2.94 2.91
Tdis [˚C] 85.5 82.0 77.8
Tsuc [˚C] 22.6 21.8 19.6
Pcond [kPa] 1768.7 2124.2 1959.6
Pevap [kPa] 712.7 736.2 699.8
Pressure ratio 2.48 2.89 2.80
Subcooling [˚C] 9.6 14.0 10.4
Superheating [˚C] 11.1 11.3 10.8
TABLE 5.18
Comparison of ASHRAE Heating 47S Test Results
Capacity [kW] 6.24 5.84 5.98

COP 3.03 2.53 2.79
Tdis [˚C] 83.2 96.5 86.3
Tsuc [˚C] 8.7 9.9 9.0
Pcond [kPa] 1793.9 2678.9 2236.6
Pevap [kPa] 507.4 502.9 483.1
Pressure ratio 3.54 5.33 4.63
Subcooling [˚C] 21.1 39.9 29.9
Superheating [˚C] 9.9 11.3 11.6
TABLE 5.19
Comparison of ASHRAE Cooling B and Heating 17L Test Results
“B” capacity [kW] 7.12 7.13 7.15

“B” COP 3.52 3.22 3.40
“17L” capacity [kW] 3.40 2.69 3.11
“17L” COP 2.09 1.59 1.87

100
R-22 Baseline
R-407C Retrofit
R-407C Path Modification
80
60
Temperature [°C]
40
20
0
Compressor Condenser Condenser Condenser Condenser Condenser TEV Evaporator Evaporator Compressor
Discharge -Inlet -1/4 -Middle -3/4 -Outlet -Inlet -Inlet -Outlet -Suction
FIGURE 5.2.7 Refrigerant temperature along the cycle in the cooling mode (Hwang et al.,
1995).
100
R-22 Baseline
R-407C Retrofit
R-407C Path Modification
80
Temperature [°C]
60
40
20
0
Compressor Condenser Condenser Condenser Condenser Condenser TEV Evaporator Evaporator Compressor
Discharge -Inlet -1/4 -Middle -3/4 -Outlet -Inlet -Inlet -Outlet -Suction
FIGURE 5.2.8 Refrigerant temperature along the cycle in the heating mode (Hwang et al.,
1995).
In this section, two sets of drop-in tests conducted by NIST are introduced. The first
set of tests was conducted with a zeotropic refrigerant, a R13B1/R152a (65/35 wt.%)
mixture in a relatively unmodified residential heat pump designed for R22 (Mulroy
and Didion, 1986). The second set of tests was conducted with two R32 mixtures,

R32/R134a and R32/R125/R134a (Rothfleisch and Didion, 1993). The following

text is based on excerpts of the above-mentioned reports. The full text is available
as NBSIR 86-3422 and NISTIR 93-5321.
5.2.2.1 R13B1/R152a Test
The purposes of the first set of tests were to investigate the potential benefits of
zeotropic mixtures in terms of thermodynamic efficiency by utilizing gliding tem-
peratures during phase change and capacity modulation by using mass fraction shift.
To fulfill these purposes, the following four tests were conducted with a nominal 3
refrigeration ton, split system, air-to-air unitary heat pump:
1. Pure retrofit tests without any modification of the test heat pump unit.
2. Simple cycle optimization tests in terms of a refrigerant charge and orifice
tube choice.
3. Effect of the zeotropic mixture mass fraction shift on the performance.
4. System with a receiver to evaluate its effect on the zeotropic mixture mass
fraction shift.
Details of the experimental results are as follows.

After the first series of tests (Test 1), it was found that the retrofit tests of mixtures
without any modifications for the system designed for R22 were not a valuable
evaluation. Considering different thermophysical properties of each refrigerant, there
was a need for system design modifications. However, minimum changes were
attempted without a major system change to pursue the retrofit option. Thus, charge
optimization and expansion device size are optional (Test 2). When optimizing the
expansion device for cooling, the degree of suction superheating should be consid-
ered for both tests condition (Test A and Test B). In general, the degree of super-
heating decreases as the ambient temperature increases. Therefore, if the degree of
superheating at Test B is insufficient, the compressor suction can be flooded at Test
A conditions. The optimization of the expansion device for heating requires main-
taining a proper degree of subcooling instead. In general, the degree of subcooling
decreases as the ambient temperature decreases. If the condenser outlet becomes
two-phase, a large amount of the refrigerant is being stored in the accumulator. This
causes a shift in the concentration of the refrigerant to contain more low boiling
refrigerant and boosts the heating capacity. Therefore, selecting an expansion device
such as subcooling at Test 47 enables the system to balance the COP at high ambient
temperature heating with increased heating capacity at low ambient temperatures.
As a simple cycle optimization for each refrigerant, two cooling tests, Test A
and Test B, and two heating tests, Test 47S (high temperature heating) and Test 17L
(low temperature heating), were performed. These tests represent the summer and
winter conditions defined by ASHRAE Standard 116, Table 5.6 (ASHRAE, 1995).
Test results are shown in Figure 5.2.9.
The optimum size of the orifice that gives a maximum capacity is different for
Test A and Test B because the cycle parameters are different depending on the
ambient temperature. For example, the optimum orifice area at Test A is 30% smaller

34000
36000
32000
22000
Capacity (Btu/hr)
34000
Capacity (Btu/hr)
Capacity (Btu/hr)
30000
32000 21000
28000
30000 20000
Binary 82°F Binary

26000 19000 Binary
Binary 95°F 28000
R22 R22
R22 82°F
9.0 R22 95°F
2.8 2.0
EER (Btuh/w)
8.0 1.9
2.7
COP
COP
7.0 2.6 1.8
6.0 2.5 1.7

.06 .07 .08 .09 .10 .11 .05 .06 .07 .08 .09 .10 .05 .06 .07 .08 .09 .10
Orifice I.D. (in) Orifice I.D. (in) Orifice I.D. (in)
(a) (b) (c)
FIGURE 5.2.9 Charge and expansion device optimization test results (Mulroy and Didion, 1986). (a) R22. (b) R32/R134a (34/66 wt.%).
(a) Test A and Test B. (b) Test 47S. (c) Test 17L.

TABLE 5.20
Comparison of Operating Pressures at Test A
Refrigerant R22 R13B1/R152a
Expansion device Capillary tube Orifice 2.0 mm Capillary tube Orifice 2.1 mm
Discharge pressure [kPa] 1917 1924 2816 2048
Discharge temperature [˚C] 111 117 105 98
Suction pressure [kPa] 572 628 571 627
Pressure ratio 3.35 3.06 3.83 3.27
Source: Mulroy and Didion, 1986.
and 6% greater than at Test B for R22 and R13B1/R152a, respectively. However,
those conditions providing the maximum COP at Test B determine the optimum
orifice size and charge since Test B has more bin hours. Another purpose of the
optimization of an expansion device is to obtain a minimal high side pressure and
subcooling. Table 5.20 compares the operating pressures of two refrigerants. As can
be seen from Table 5.20, the cycle with an optimized orifice has a pressure ratio
reduced by 9 and 15% as compared to the drop-in tests with a capillary tube for
R22 and R13B1/R152a, respectively. The suction pressure increases for the orifice
cases due to the reduced degree of superheating at the evaporator outlet as an outcome
of an orifice size optimization. The discharge temperature of R13B1/R152a is about
10 K lower than that of R22, as shown in Table 5.20.
As can be seen from Figure 5.2.9, the performance of the R13B1/R152a mixture
was lower than that of R22 in general: a 3% loss in COP for Test 47S, a 12% loss
in capacity and 11% loss in COP for the cooling test, except a 6% improvement in
capacity and no change in COP for Test 17L (–8.3˚C). One of the reasons for this
performance degradation is an inability to utilize a temperature glide of the zeotropic
mixtures. There are two barriers to utilize the temperature glide of zeotropic mixtures
in an air-to-air heat pump or air conditioner: the crossflow heat exchange configu-
ration for the most widely accepted heat exchangers and the refrigerant flow reversal
when switching the operating mode from cooling to heating for heat pumps. The
second reason is that these tests were conducted on a drop-in basis without any
major system modification.
To increase the heating capacity at low ambient temperatures, it was necessary
to sacrifice the subcooling at the condenser outlet. To investigate the performance
potential of the R13B1/R152a mixture with subcooling and a large mass fraction
shift, a high mass fraction test was conducted by charging a premixed mixture at
86% of R13B1. This investigation of the mass fraction shift on the capacity modu-
lation showed that the heating capacity at –8.3˚C increased 18% above that with
R22 when the R13B1 mass fraction was 86% (Table 5.21). This mass fraction shift
strategy would contribute to increased seasonal performance in cold climates by
reducing the need for electric heat.
To realize this benefit, a receiver was added in the liquid line to create a mass
fraction shift at low air temperatures. The volume of the receiver was 2.3 l, which

TABLE 5.21
Performance of High R13B1 Mass Fraction
Refrigerant R22 R13B1/R152a (86/14 wt.%)
Ambient temperature [˚C] –8.3 –8.3 47

Capacity [kW] 6.3 7.4 11.5
COP 1.98 2.00 2.41
Discharge pressure [kPa] 1241 1786 2124
Discharge temperature [˚C] 100 81 78
Suction pressure [kPa] 296 425 665
Source: Mulroy and Didion, 1986.
could store 2.6 kg of R22 or R13B1/R152a (65/35 wt.%) mixture if completely

filled. This extra amount of refrigerant in the receiver during steady-state operations
resulted in a total system charge that would overfill the accumulator during cyclic
operation. This large mass fraction shift to the higher mass fraction of R13B1 resulted
in a large volumetric capacity by increasing the suction vapor density. Indeed this
option enhances the control over the mass fraction shift by adding one more degree
of freedom in terms of refrigerant storage, resulting in a 14 and 2% capacity and
COP increase, respectively, at the –8.3˚C rating point.
Mixtures should be evaluated on a reliability basis as well as energy performance.
For the vapor compression cycle, this usually means consideration of the discharge
pressure and temperature levels as well as the pressure difference and ratio. For a
heat pump, the high-stress condition resulting from high pressures and temperatures
will occur during the highest condenser operating conditions, which corresponds
with the cooling mode.
Conclusions
• Retrofit of R22 by R13B1/R152a mixtures improved low temperature
heating capacity up to 6%, but lost in high temperature heating COP by
3%, in cooling capacity by 12% and in cooling COP by 11%.
• Mass fraction shift effectively controls the heating capacity and showed
18% higher low temperature heating capacity than that of R22.
• A liquid line receiver enhanced the control over the mass fraction shift
and resulted in 14 and 2% low temperature heating capacity and COP
increases, respectively.
• Both energy performance and reliability should be emphasized for mixtures.
5.2.2.2 R32/R134a Test

The second set of tests was conducted with R32/R134a (34/66 wt.%). The purpose
of this study was to experimentally evaluate a drop-in performance of R32/R134a
and a performance of the cycle with SLHX. The mass fraction of R32/R134a was
chosen such that the vapor pressure of this mixture is similar to that of R22.

Moreover, the performance of this binary mixture has shown an equivalent perfor-
mance to that of R22 with a counter flow heat exchange configuration (Rothfleisch
and Didion, 1993).
Retrofit Test of R32/R134a
Similar to the tests for R13B1/R152a, a retrofit test was conducted with an optimi-
zation of the expansion device opening and refrigerant charge at ASHRAE Test A
condition. The optimum combination of expansion device opening and refrigerant
charge were determined when that combination yields the maximum COP. The
system was then tested at ASHRAE Test B condition with the optimum combination
determined from Test A.
In general, the residential heat pumps have two expansion devices, one for
cooling and the other for heating. The second optimization for the heating mode
was conducted at the ASHRAE Test 47S condition similar to the cooling mode
optimization.
The results of the cooling mode optimization are shown for R22 and R32/R134a
in Figure 5.2.10. In these tests, the degree of subcooling was adjusted by changing
the refrigerant charge and the degree of superheating at the evaporator outlet was
adjusted by the expansion valve opening between 1.7 and 2.8˚C. The highest capacity
was obtained at a minimum of superheating. Therefore, for each value of subcooling,
the expansion valve opening was optimized. The optimum values of subcooling were
approximately 5.6 and 2.8˚C for R22 and R32/R134a, respectively, as shown in
Figure 5.2.10.
The same optimization procedures applied for the heating mode. The results of
the heating mode optimization for R22 showed that there was no definite maximum
at various values of the subcooling, as shown in Figure 5.2.11. As can be seen from
this result, the maximum COP is achievable when the subcooling becomes zero.
However, the degree of subcooling decreases as the ambient temperature drops.
Therefore, if the subcooling were set to zero at Test 47S conditions, the condenser
outlet would be two-phase at Test 17L conditions. When the ambient temperature
drops, the heating load increases but the heating capacity decreases. If the condenser
outlet became two-phase, the heating capacity would further decrease. Therefore,
the heating optimization should be conducted while balancing the heating COP at the
high ambient temperature and the heating capacity at the low ambient temperature.
Figures 5.2.12 through 5.2.14 show the effect of subcooling on the capacity,
COP and condensing pressure. As the subcooling increases, the capacity increases
since the latent heat of evaporation increases due to the lower evaporator inlet
enthalpy. As the subcooling increases, the power increases since the condensing
pressure increases as shown in Figure 5.2.14. The reason the condensing pressure
increases is that as the subcooling increases, a smaller portion of the condenser is
used for the two-phase and superheated gas heat transfer.
The only way to maintain the same capacity or even increase capacity is to
increase the temperature difference if the condenser UA is constant. In other words,
the condensing temperature and condensing pressure increase and result in an
increased pressure ratio. When the compression pressure ratio increases, the com-
pressor delivers less mass flow rate and the power per unit refrigerant mass increases.
3.46
3.44
3.42
COP
3.4
3.38
3.36
3.34
1.7 2.8 3.9 5 6.1 7.2 8.3 9.4
(3) (5) (7) (9) (11) (13) (15) (17)
Subcooling °C (°F)
(a)
3.1
3.08
3.06
3.04
3.02
COP
2.98
2.96
2.94
2.92
1.1 2.2 3.3 4.4 5.8 6.7 7.8 8.9 10
(2) (4) (6) (8) (10) (12) (14) (16) (18)
(b)
FIGURE 5.2.10 Cooling mode optimization (Rothfleisch and Didion, 1993).

3.92
3.9
3.88
3.86
3.84
COP
3.82
3.8
3.78
3.76
3.74
1.7 2.6 3.9 5 6.1 7.2
(3) (5) (7) (9) (11) (13)
FIGURE 5.2.11 Heating mode optimization for R22; x-flow: crossflow, x-para: cross-parallel
flow (Rothfleisch and Didion, 1993).
In summary, there are two competing effects to be balanced: a positive effect on the
COP by a larger latent heat and a negative effect by an increased condensing pressure.
One important characteristic of the R32/R134a mixture obtained from these
figures is that the capacity of R32/R134a increases slower than that of R22 while
the power increases faster than that of R22 when the subcooling increases. This fact
means the optimum COP of R32/R134a occurs at a lower subcooling than that of
R22. This feature can be understood from the vapor pressure curve of these two
refrigerants. R32/R134a has a greater slope than that of R22; therefore, the greater
slope of R32/R134a causes a faster condensing pressure increase than R22 at the
same temperature increase.
Since the retrofit approach was used in this study, the heat exchanger configu-
ration was the same for the two refrigerants but it changed from crossflow (referred
to as x-flow) to cross-parallel flow (referred to as x-para) when the operating mode
switched from cooling to heating. There was a definite optimum point for R22
cooling optimization results but no optimum point for the R22 heating optimization
results, as shown in Figures 5.2.10 and 5.2.11.
Since these tests were done for the same R22, the different results are believed
due to the difference in the condenser configuration. In fact, with help from Figures
5.2.12 through 5.2.14, one can explain this phenomenon. The outlet refrigerant of
the cross-parallel flow heat exchanger will approach the exiting air temperature while
that of the crossflow heat exchanger will approach the entering air temperature.
(9) 2.64
Capacity kW (kBtu/h)
(8.8) 2.58
(8.6) 2.52
(8.4) 2.46
(8.2) 2.40
(8) 2.34
1.7 2.8 3.9 5 6.1 7.2 8.3 9.4 10.6
(3) (5) (7) (9) (11) (13) (15) (17) (19)
R22 Cool (x-flow) R22 Heat (x-para) mtx Cool(x-flow)
FIGURE 5.2.12 Capacity vs. subcooling; x-flow: crossflow, x-para: cross-parallel flow (Roth-
fleisch and Didion, 1993).
840
820
800
780 A
Power (watts)
760
B
740
720
700
680 C
660
1.7 2.8 3.9 5 6.1 7.2 8.3 9.4 10.6
(3) (5) (7) (9) (11) (13) (15) (17) (19)
R22 Cool (x-flow) R22 Heat (x-para) Mix Cool (x-flow)
FIGURE 5.2.13 Power vs. subcooling; x-flow: crossflow, x-para: cross-parallel flow (Roth-
fleisch and Didion, 1993).
Therefore, the condenser outlet refrigerant temperature in the heating mode should
be higher than that in the cooling mode since the approach temperature cannot be
negative. The condensing temperature in the heating mode should then be higher
than that in the cooling mode when the same degree of subcooling is maintained.
This reason is why the power and condensing pressure in the heating mode increases
faster than in the cooling mode.
(310) 2137
Condenser pressure kPa (psia)

(290) 1999
A
(270) 1862
B
(250) 1724
(230) 1586
1.7 2.8 3.9 5 6.1 7.2 8.3 9.4 10.6
(3) (5) (7) (9) (11) (13) (15) (17) (19)
R22 cool (x-flow) R22 heat (x-para) Mix cool (x-flow)
FIGURE 5.2.14 Condensing pressure vs. subcooling (Rothfleisch and Didion, 1993).
TABLE 5.22
Retrofit Performance of R32/R134a as compared to R22
Test Condition [˚C] Normalized Capacity Normalized COP Normalized Power
Cooling test A [35] 0.93 0.89 1.04

Cooling test B [27.8] 0.94 0.90 1.05
Heating test 47S [8.3] 0.93 0.91 1.02
Heating test 17L [–8.3] 1.04 0.90 1.16
Source: Rothfleisch and Didion, 1993.
The retrofit performance data of R32/R134a normalized by R22 results for the
same test are summarized in Table 5.22. This table shows the lower capacity and
COP by about 6 to 10% but the heating capacity increases 4% at the –8.3˚C heating
test due to the passive mass fraction shift.
One of the reasons for the lower performance of R32/R134a is due to the lower
volumetric capacity of R32/R134a. The latent heat of R32/R134a was 17% higher
than that of R22 but the suction density was 21% lower than that of R22 for the
cooling Test A condition, which resulted in an 8% lower volumetric capacity. Figure
5.2.15 compares two refrigerant cycles in the ln(P)-h diagram. From Figure 5.2.15,
a higher condensing pressure and larger latent heat of evaporation of R32/R134a
than those of R22 can be easily recognized.
SLHX Test of R32/R134a
To investigate the cycle options for the R32/R134a mixture performance improve-
ment, further tests with SLHX were conducted in the cooling mode. The low-pressure
(300) 2068
Absolute Pressure kPa (paia) (260) 1793
(220) 1517
(180) 1241
(140) 965
(100) 689
(60) 414
(20) 138
0 47 93 140 186 233 279 326 372
(0) (20) (40) (60) (80) (100) (120) (140) (160)
Enthalpy kJ/kg (Btu/lb)
34% R32/66% R134a R22
FIGURE 5.2.15 P-h diagram of R22 and R32/R134a (34/66 wt.%) (Rothfleisch and Didion,
1993).
Bottom Circuit EVAP Temp Profile Top Circuit EVAP Temp Profile
35°C (95°F) Cooling 35°C (95°F) Cooling
(60) 15.6 (74) 23.3
(58) 14.4
(70) 21.1
Temperature °C (°F)
(56) 13.3
Temperature °C (°F)
(54) 12.2 (66) 18.9

(52) 11.1 (62) 16.7
(50) 10 (58) 14.4
(48) 8.9 (54) 12.2
(46) 7.8
(44) 6.7 (50) 10
(42) 5.6 (46) 7.8
(40) 4.4 (42) 5.6
1 3 5 7 9 11 13 15 17 19 1 3 5 7 9 11 13 15 17 19
Position Position
R22 34% R32/68% R134a LL-SL HX (2 Phase) R22 34% R32/66% R134a LL-SL HX (2 Phase)
FIGURE 5.2.16 Evaporator temperature profile of R22 and R32/R134a (34/66 wt.%). (a)
Bottom circuit. (b) top circuit. (Rothfleisch and Didion, 1993).
inlet side of the SLHX can be either single-phase or two-phase by adjusting the
expansion valve. Both test results at Test A and B conditions are summarized in
Table 5.23. From the test results, the SLHX cycle with optimized expansion valve
opening at Test A condition showed a performance degradation at Test B condition,
even worse than without SLHX.
For the cycle without SLHX, the refrigerant migrates from the evaporator to the
condenser when the ambient temperature drops since the compressor delivers more
TABLE 5.23
SLHX Performance of R32/R134a as compared to R22
Refrigerant Phase
Entering Low-pressure Normalized Normalized Normalized
Test Condition [˚C] Side of SLHX Capacity COP Power
Cooling test A [35] No SLHX 0.93 0.89 1.04

1 phase 0.95 0.90 1.05
2 phase 0.96 0.91 1.06
2 phasea 0.95 0.90 1.06
Cooling test B [27.8] No SLHX 0.94 0.90 1.05
1 phase 0.91 0.87 1.04
2 phase 0.92 0.88 1.04
2 phasea 0.97 0.92 1.05
Note: The expansion valve was adjusted at the 35˚C test condition.
a The expansion valve was adjusted at the 27.8˚C test condition.
Source: Rothfleisch and Didion, 1993.
refrigerants to the condenser, while the expansion device further limits the refrigerant
flow due to the reduced pressure ratio. For the cycle with SLHX, the refrigerant
flow through the expansion valve is limited due to the increased subcooling by the
SLHX, which contributes to the lower performance. When the expansion valves
were adjusted at Test B (27.8˚C) condition, the performance was improved for Test B
while Test A had an identical performance.
Conclusions
• The heating optimization should be conducted while balancing the heating
COP at the high ambient temperature and the heating capacity at the low
ambient temperature.
• The compressor power increases as the degree of subcooling increases.
The capacity of R32/R134a increases slower than that of R22, while the
power increases faster than that of R22 when the subcooling increases.
This fact means the optimum COP of R32/R134a occurs at lower sub-
cooling than that of R22.
• The retrofit performance of R32/R134a showed the lower capacity and
COP than those of R22 by about 6 to 10%. The heating capacity increased
by 4% at the –8.3˚C heating test due to the passive mass fraction shift.
• The SLHX cycle with optimized expansion valve opening at Test A
condition showed a performance degradation at Test B condition, even
worse than without SLHX. When the expansion valves were adjusted at
Test B (27.8˚C) condition, the performance was improved for Test B while
Test A had an identical performance.
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Heat Pump Equipment,” ARI Standard 210/240.
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ASHRAE Handbook of Fundamentals, 1985, Chapter 16, “Refrigerants,” American Society
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Calm J.M., 1995, “Refrigerants and Lubricants Data for Screening and Application,”
Proceedings of the 1995 International CFC and Halon Alternatives Conference, Wash-
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Conklin, J.C. and E.A. Vineyard, 1991, “Cycle Performance Comparison between a Non-
azeotropic Refrigerant Mixture and R22,” Proceedings of XVIIIth International
Congress of Refrigeration, Vol. III, pp. 1270–1274.
Didion, D.A. and D. Bivens, 1989, “The Role of Refrigerant Mixtures as Alternatives,” CFC
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Domanski, P.A. and M.O. McLinden, 1992, “A Simplified Cycle Simulation Model for the
Performance Rating of Refrigerants and Refrigerant Mixtures,” International Journal
of Refrigeration, Vol. 15, No. 2.
DuPont, 1994, Suva Refrigerants Technical Information.
DuPont, 1995, Suva Alternative Refrigerants Technical Information.
Gallagher, J., M. McLinden, and M. Huber, 1993, REFPROP NIST Thermodynamic Proper-
ties of Refrigerants and Refrigerant Mixtures Database, Version 4.01, Thermophysics
Division of National Institute of Standards and Technology, Gaithersburg, MD.
Godwin, D., 1993, “Results of System Drop-In Tests in ARI’s R-22 Alternative Refrigerants
Evaluation Program,” ARI, Arlington, VA.
Hwang, Y., J. Judge, and R. Radermacher, 1995, “An Experimental Evaluation of Medium
and High Pressure HFC Replacements for R22,” Proceedings of the 1995 International
CFC and Halon Alternatives Conference, Washington D.C., pp. 41–48.
Kauffeld, M., W. Mulroy, M. McLinden, and D. Didion, 1990, “An Experimental Evaluation
of Two Nonazeotropic Refrigerant Mixtures in a Water-To-Water, Breadboard Heat
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burg, MD.
Kolliopoulos, K.G., 1994, “Update on Developmental HFC Replacements for HCFC-22,”
Presented at the 1994 International CFC and Halon Alternatives Conference, Wash-
ington, D.C.
Kruse, H., 1980, “The Advantages of Non-Azeotorpic Refrigerant Mixtures for Heat Pump
Application,” Mons (Belgium) Meeting of Commissions D1, D2, E1 and E2 of the
IIR.
McLinden, M. and R. Radermacher, 1987, “Methods for Comparing the Performance of Pure
and Mixed Refrigerants in the Vapor Compression Cycle,” International Journal of
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Morrison, G. and M. McLinden, 1986, “Application of a Hard Sphere Equation of State to
Refrigerants and Refrigerant Mixtures,” NBS Technical Note 1226, National Institute
of Standards and Technology, Gaithersburg, MD.
Mulroy, W. and D.A. Didion, 1986, “The Performance of a Conventional Residential Sized
Heat Pump Operating with a Nonazeotropic Binary Refrigerant Mixture,” NBSIR
86-3422, National Institute of Standards and Technology, Gaithersburg, MD.
Mulroy, W., M. Kauffeld, M. McLinden, and D.A. Didion, 1988, “An Evaluation of Two
Refrigerant Mixtures in a Breadboard Air Conditioner,” Proceedings of the IIR Con-
ference at Purdue, West Lafayette, IN.
Mulroy, W., M. Kauffeld, M. McLinden and D.A. Didion, 1988, “Experimental Evaluation
of Two Refrigerant Mixtures in a Breadboard Air Conditioner,” Proceedings of the
2nd DOE/ORNL Heat Pump Conference, CONF-8804100.
Pannock, J. and D.A. Didion, 1991, “The Performance of Chlorine-Free Binary Zeotropic
Refrigerant Mixtures in a Heat Pump,” NISTIR 4748, National Institute of Standards
and Technology, Gaithersburg, MD.
Quast, U. and H. Kruse, 1986, “Experimental Performance Analysis of a Reciprocating
Compressor Working with Non-Azeotropic Refrigerant Mixtures,” Proceedings of
the International Compressor Engineering Conference at Purdue, West Lafayette, IN.
Radermacher, R., 1986, “Advanced Versions of Heat Pump with Zeotropic Refrigerant Mix-
tures,” ASHRAE Transactions, Vol. 92, Pt. 2, pp. 52–59.
Rothfleisch, P.I. and D.A. Didion, 1991, “A Performance Evaluation of a Variable Speed,
Mixed Refrigerant Heat Pump,” NISTIR 93-5321, National Institute of Standards and
Technology, Gaithersburg, MD.
Rothfleisch, P.I. and D.A. Didion, 1993, “A Study of Heat Pump Performance Using Mixtures
of R32/R134a and R32/R125/R134a as Drop-In Working Fluids for R22 with and
without a Liquid-Suction Heat Exchanger, NISTIR 5321, National Institute of Stan-
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Compression Cycle Device,” United States Patent No. 4034099.
Vineyard, E.A, 1988, “Laboratory Testing of a Heat Pump System Using an R13B1/R152a
Refrigerant Mixture,” ASHRAE Transactions, Vol. 94, Pt. 1, pp. 292–303.
Vineyard, E.A. and J.C. Conklin, 1991, “Cycle Performance Comparison between a Non-
azeotropic Refrigerant Mixture and R22,” Proceedings of XVIIIth International Con-
gress of Refrigeration, Vol. II, pp. 543–547.
Vineyard, E.A. and J.C. Conklin, 1993, “Cycle Performance Testing of Nonazeotropic
Mixtures of HFC32/HFC124 with Enhanced Surface Heat Exchangers,” ASHRAE
Vineyard, E.A., J.C. Conklin, and A.J. Brown, 1993, “Cycle Performance Testing of Non-
azeotropic Mixtures of HFC-143a/HCFC-124 and HFC32/HCFC124 with Enhanced
Surface Heat Exchangers, ASHRAE Transactions, Vol. 99, Pt. 2, pp. 97–103.
6 Refrigerant Mixtures
in Refrigeration
Applications
As the global economy and technology have improved dramatically since World
War II, the demand for human comfort has resulted in an increased demand for
household refrigerators and freezers. Energy usage has increased also by the
increased use of energy-consuming products. This change of lifestyle generates the
demand to provide additional refrigeration capacity with increased energy efficiency.
The introduction of refrigerant mixtures was considered mainly due to the increased
demand of the larger refrigeration capacity, the better control of two evaporator
temperature levels and the potential of improved energy efficiency. Refrigerators
with two temperature levels were considered good applications for refrigerant mix-
tures because of one main inherent thermodynamic irreversibility: in conventional
refrigerators and freezers, the higher temperature food compartment is cooled by an
evaporator operating on the freezer temperature level.
6.1 SINGLE EVAPORATOR REFRIGERATION CYCLE

Refrigerators or freezers with single evaporator and one temperature level compart-
ment (SEOC) utilize the refrigeration cycle as shown in Figure 3.3.1. A T-s diagram
of the SEOC is shown in Figure 3.4.1(a). The dotted line (1A–4A) is the air
temperature of the refrigerating or freezing compartment as it varies along the length
of the evaporator. The dotted line (3A–2A) is the air temperature across the condenser
as it varies along the length of the condenser.
Most of household refrigeration machines are a combination of refrigerators and
freezers used to maintain two low temperature levels. The lowest temperature level
compartment is called the “freezer compartment” and the other compartment has a
higher temperature and is called the “food compartment.” Typical compartment
temperatures are about –15ºC for the freezer compartment and about 3ºC for the
food compartment. Refrigerator and freezers with a single evaporator and two
temperature level compartments (SETC) utilize the same refrigeration cycle as that
of SEOC. Conventional refrigerators and freezers with a single evaporator then
employ a damper to control the degree of heat exchange between the compartments,
as shown in Figure 6.1.1. A T-s diagram of SETC is shown in Figure 6.1.2. Dotted
lines (1A–4′A and 3A–2′A) are air temperatures across the evaporator and condenser,
respectively, which vary along the length of the heat exchangers for counter-current
heat exchange.
209
Condenser
3 2'
3A 2'A
Expansion Compressor
Device 4'A 5A
Airflow paths
Damper 4'A 6A
4'A 1A
4' 1
Evaporator
FIGURE 6.1.1 Single evaporator refrigeration cycle with two temperature level compartments.
Refrigerating capacity
Lost expansion work
2'
Work due to superheating
P1
Temperature (T)
3 2
3A 2'A
1A
4'A
1
4 4'
P2 Q
Entropy (s)
FIGURE 6.1.2 T-s diagram of single evaporator refrigeration cycle with two temperature
level compartments.
To maintain the temperature in the freezer compartment at the desired level, the
low evaporation temperature must also be used to cool the food compartment. Thus,
the temperature lift, the temperature difference between the condenser and the
evaporator, is necessarily greater for the SETC than for the appliances with SEOC.
The inherent problem with SETC is that it does not take advantage of the smaller
temperature lift available for the food compartment, resulting in a lower overall
COP. The main reasons for employing the SETC concept are space, cost savings
and excellent reliability. Since the Montreal Protocol declared a ban on CFCs
(chlorofluorocarbons) used as refrigerants and foaming agents of refrigeration sys-
tems, there has been an effort to find CFC substitutes for the single evaporator
refrigeration cycle.
Refrigerant Mixtures in Refrigeration Applications 211
TABLE 6.1
Simulation Results of Refrigerants Examined
Volumetric Mixed Volumetric
Pure Refrigerant COP Capacity [kg/m3] Refrigerant COP Capacity [kg/m3]
R11 1.15 49 R22/152a 1.37 851

R12 1.35 769 R22/142b 1.39 706
R13B1 1.28 1964 R22/134a 1.35 1115
R22 1.35 1247 R22/134 1.36 839
R32 1.34 2047 R22/123 1.31 168
R114 1.25 182 R32/152a 1.38 1001
R123 1.15 42 R32/142b 1.41 544
R124 1.32 406 R32/134a 1.35 1170
R125 1.24 1580 R32/134 1.36 862
R134 1.33 545 R125/152a 1.36 671
R134a 1.33 715 R125/142b 1.39 499
R141b 1.35 77 R125/141b 1.40 127
R142b 1.36 367 R125/134a 1.33 715
R143a 1.29 1464 R125/134 1.34 670
R152a 1.36 671 R125/123 1.28 100
R143a/152a 1.36 671
R143a/142b 1.39 528
R143a/141b 1.41 140
R143a/134a 1.33 777
R143a/134 1.34 694
R143a/123 1.29 116
Source: Jung and Radermacher, 1991.
Stocker and Walukas simulated the performance of the SETC with R12/R114
mixtures (1981). In their model, the condenser outlet and the evaporator outlet were
assumed to be a saturated liquid and vapor, respectively. In their study, they showed
when the mass fraction of R114 is 0.5, the power consumption is 11% less than
when the mass fraction of R114 is 0.01.
As a preliminary study to screen potential alternative refrigerants, Jung and
Radermacher (1991) presented their simulation results for 15 pure and 21 mixed
refrigerants. A list of refrigerants examined with results are shown in Table 6.1.
Based on these results, they concluded that there is no drop-in pure refrigerant
because R134, R134a and R152a have a 7 to 30% lower capacity than R12. More-
over, R22, R32, R152a and R142b have comparable COPs to R12 but have far
different capacities than R12. As drop-in refrigerants, they recommended R22/R142b,
R22/R152a and R32/R142b.
In an experimental effort, Vineyard et al. (1989) investigated the energy-saving
potential of five refrigerants: R12, R500, R12/dimethylether (DME), R22/R142b
and R134a. From their drop-in tests for these five refrigerants in a 0.5 m3 top-mount
refrigerator-freezer, they found that azeotropic mixtures, R500 and R12/DME saved
about 6% on energy consumption, while R134a and R22/R142b showed about 8%

higher energy consumption.
Zhang et al. (1992) investigated the performance potential of a ternary mixture,
R22/R114/R152a (36/40/24 wt.%). The motivation of this study was to reduce the
use of CFCs. Zhang et al. also experimentally compared the performance of R152a
with R12 while keeping the structure of the refrigerator and only optimizing the
charge for each refrigerant. They found that R152a could reduce the energy con-
sumption by 10% over R12; however, they also found that the evaporating temper-
ature is about 7 K higher than that of R12. To match the evaporating temperature
as a retrofit refrigerant of R12 and decrease the flammability of R152a, Zhang et al.
tried to mix R152a with R22. They found that R22/R152a has a lower evaporating
temperature than R152a but is still 4 K higher than that of R12 but the energy
consumption of R22/R152a is 2% higher than R12. Therefore, R22/R152a does not
have any advantage in terms of energy savings. They then investigated
R22/R114/R152a to take advantage of R152a’s properties and avoid any flamma-
bility issues of R152a by mixing it with R22 and R114. They found that the energy
consumption of R22/R114/R152a mixture is 3% lower than that of R12.
The Montreal Protocol aims not just at reducing the use of CFCs but banning
their use entirely. Therefore, the R22/R114/R152a mixture cannot be an ultimate
solution because it contains R114. For a solution to this problem, Kuijpers et al.
(1990) investigated the performance potential of a ternary mixture, R22/R124/R152a
(28/40/32 wt.%). Another motivation of Kuijpers’ study was to avoid the perceived
energy penalty of R134a, regarded as one of the alternatives of R12. They found
that the COP of R22/R124/R152a mixture is 6% higher than that of R12 when the
evaporation temperature is between –15 and –25˚C.
6.2 DUAL EVAPORATOR REFRIGERATION CYCLE

Refrigerator-freezers with dual evaporators and two temperature level compartments
(DETC) utilize the refrigeration cycle as shown in Figure 6.2.1. These devices have
separate compartments, each fitted with an evaporator: the freezer compartment with
Condenser
3 2'
3A 2'A
Device 4'A 5A 6A 1A
4' 1
5
1st Evaporator 2nd Evaporator
FIGURE 6.2.1 Dual evaporator refrigeration cycle with two temperature level compartments.
Lost expansion work 2'
Additional work
P1
Temperature (T)
3 2
3A 2'A
6 6A 7A
4'A 5A 7
P3
4 4' 5 1
P2 Q
Entropy (s)
FIGURE 6.2.2 T-s diagram of dual evaporator refrigeration cycle with two temperature level
compartments.
the first evaporator and the food compartment with the second evaporator. A T-s
diagram of SETC is shown in Figure 6.2.2. Dotted lines (5A–4′A and 7A–6A) are
air temperatures of the freezer compartment and the food compartment, respectively,
that vary along the length of the first and second evaporators. The dotted line
(3A–2′A) is the air temperature along the condenser. The requirement of having two
separate compartment temperatures results in an additional loss for dual-evaporator
refrigeration systems as clearly represented by the area P3. As for the SETC, the
lower evaporation temperature must be used for the food compartment also in order
to maintain the lower temperature in the freezer compartment. The inherent problem
with DETC is the same as that of SETC, resulting in a low overall COP.
6.3 LORENZ-MEUTZNER CYCLE

There has been an effort to improve the disadvantage of the single evaporator
refrigeration cycle by implementing the Lorenz refrigeration cycle using refrigerant
mixtures. Figure 6.3.1 shows the T-s diagram of the Lorenz cycle with DETC. This
figure shows the same benefit of the Lorenz refrigeration cycle over the Rankine
refrigeration cycle for SEOC.
The second major effort to improve the disadvantage of the single evaporator
refrigeration cycle uses the dual-evaporator refrigeration cycle. Lorenz and Meutzner
(1975) proposed a dual evaporator refrigeration cycle with two inter-coolers using
zeotropic refrigerant mixtures, as shown in Figure 6.3.2. In this cycle, the condenser
outlet is connected to the suction heat exchanger that exchanges heat with the suction
line. The liquid outlet of the suction heat exchanger is connected to an internal heat
exchanger that subcools the liquid heater with the evaporating refrigerant as it passes
between the evaporators. The outlet of the internal heat exchanger is connected to
the expansion device.
P1
Temperature (T)
2
3
2'A
P3
3A 6A
5A 1A
4'A 1
4 4' 5
P3 Q
Entropy (s)
FIGURE 6.3.1 T-s diagram of dual evaporator Lorenz cycle with two temperature level
compartments.
Condenser
3 2'
3A 2'A
3I
3II Compressor
Internal Suction-Line
Heat Exchanger Heat Exchanger
Expansion 1
Device
4'A 5A 6A 7A
4' 7
56
FIGURE 6.3.2 Lorenz-Meutzner cycle.
The expanded two-phase refrigerant from the expansion device enters the evap-
orator and then passes through the internal heat exchanger, the food temperature
evaporator and the suction heat exchanger, sequentially. Therefore, the internal heat
exchanger and suction line heat exchanger offer more subcooling at the condenser
outlet and at the same time take advantage of and provide an appropriate temperature
glide for both evaporators. Figure 6.3.3 shows the T-s diagram of the Lorenz-
Meutzner cycle. Here the additional work requirement, area P3 of Figure 6.3.1, is
not present because the refrigerant entering the refrigerator evaporator is heated by
P1
Te mperature (T)
2
3
3I 2'A
3II 3A
7A
4'A 5A 6A
1
4' 5 6 7
4
P2 Q1 Q2
Entropy (s)
FIGURE 6.3.3 T-s diagram of a Lorenz-Meutzner cycle.
the second heat exchanger from T5 to T6. Therefore, an approach temperature between
the air and refrigerant of the second evaporator is reduced. With the addition of a
food compartment evaporator and the use of a well-chosen zeotropic refrigerant
mixture, evaporation at two temperature levels in a single refrigeration cycle can be
achieved with a higher COP than the conventional vapor compression refrigeration
cycle. This is the concept upon which the Lorenz-Meutzner cycle is based.
Lorenz and Meutzner reported a 20% energy savings for a Lorenz-Meutzner
cycle with a mixture of R22/R11 (50/50 wt.%) compared to a conventional refrig-
erator with R12. Stoecker and Walukas (1981) showed no energy savings for a
mixture of R12/R114 (50/50 wt.%) but they reported that the simulated power of
the Lorenz-Meutzner cycle with the R12/R114 mixture (50/50 wt.%) was 12% less
than that of R12. In their study, they showed that when the mass fraction of R114
is 0.5, the power consumption is 11% less than when the mass fraction of R114 is
0.01. Tiedemann et al. (1991) tested various mixtures but did not find any savings.
The experimental results of Rose et al. (1992) showed a 9% reduction in energy
consumption with a zeotropic mixture of R22/R123. Sand et al. (1993) found that
the Lorenz-Meutzner cycle with R32/R124 mixtures (15/85 wt.%) saved 6 to 7% energy
use over R12. They also emphasized the importance of counterflow, refrigerant-to-
air heat exchangers.
6.4 MODIFIED LORENZ-MEUTZNER CYCLE REFRIGERATOR

The Lorenz-Meutzner cycle utilizes two internal heat exchangers to reduce the
approach temperature between the refrigerant and air streams at the freezer and food
compartments by subcooling the liquid refrigerant before the expansion process.
Radermacher and Jung (1993a) presented a modified version of the Lorenz-Meutzner
cycle that further subcools the liquid refrigerant before the expansion process by
extending the high pressure liquid line through the first and second evaporators, as
Condenser
3 2'
3A 2'A Compressor
Suction-Line
1
Heat Exchanger
4'A 5A 6A 7A
5 6
4' 7
Expansion 8
Device 10 9
11 2nd Internal
Heat Exchanger
FIGURE 6.4.1 Modified Lorenz-Meutzner cycle.
P1
Te mperature (T)
2
3
2'A
98
10 3A
11 7A
4'A 5A 6A
1
4' 5 6 7
4
P2 Q1 Q2
Entropy (s)
FIGURE 6.4.2 T-s diagram of a modified Lorenz-Meutzner cycle.
shown in Figure 6.4.1. This is an example for implementing the three paths evapo-
rator design that is discussed in Chapter 4. The difference between the Lorenz-
Meutzner cycle and the modified Lorenz-Meutzner cycle is shown in the T-s diagram
of the modified Lorenz-Meutzner cycle refrigerator, Figure 6.4.2. The modified Lorenz-
Meutzner cycle refrigerator has a four step subcooling process, while the
Lorenz-Meutzner cycle refrigerator has only two steps of subcooling. In the modified
Lorenz-Meutzner cycle, the first and second evaporators serve as three-way heat
exchangers made by a smaller tube (liquid line) inserted into a larger tube (suction
line and evaporator). The compartment air surrounding the bigger tube and subcooled
liquid in the smaller tube rejects heat to the two-phase refrigerant running counterflow
through the annulus of the two tubes. Zhou et al. (1994) reported 16.6, 14.6 and
16.7% energy savings from their experiments with a modified-Lorenz-Meutzner
cycle refrigerator with zeotropic mixtures R22/R123, R290/n-pentane and R290/R600,
respectively. The conventional SETC uses a damper to control the food compartment
temperature and a thermostat to control the freezer compartment temperature. The
main purpose of the dual evaporators is to provide better temperature control.
For the Lorenz-Meutzner cycle, however, independent temperature control of
the two compartments is not as simple since there is no damper. The temperature
conditions of both compartments compared to their temperature settings determine
the operation of the compressor. Therefore, one compartment temperature can be
dropped further than the set temperature when the other compartment temperature is
higher than the temperature set point. In this case, failure of implementing indepen-
dent temperature control results in an energy loss. Simmons et al. (1995) suggested
an independent temperature control of compartments in a modified Lorenz-Meutzner
cycle by using a bistable solenoid valve as shown in Figure 6.4.3. The suggested
control of a modified Lorenz-Meutzner cycle directs refrigerant through alternate
evaporator paths with a bistable solenoid valve that regulates the entire flow of
refrigerant to only the freezer evaporator or to both evaporators.
When the bistable solenoid valve is at position A (Mode A), the cycle becomes
a modified Lorenz-Meutzner cycle as shown in Figure 6.4.3. When the bistable
solenoid valve is at position B (Mode B), the cycle becomes SEOC with two serial
suction line heat exchangers. When both compartments need cooling, the bistable
valve switches to Mode A. When only the freezer compartment needs cooling, the
bistable valve switches to Mode B. Therefore, the suggested control method for a
modified Lorenz-Meutzner cycle provides a similar independent temperature control
to the SETC with the damper.
Condenser
3 2'
3A 2'A
Bistable Solenoid Valve B A
3I Compressor
3II
5I
1st Internal Suction-Line
1
Expansion Heat Exchanger Heat Exchanger
5"
Device B
4'A 5A
6A 7A
4" 5 6
4' 7
Expansion 8
Device A 10 9
11 2nd Internal
Heat Exchanger
FIGURE 6.4.3 Modified Lorenz-Meutzner cycle with bistable solenoid valve.

Simmons et al. (1995) experimentally demonstrated that the modified Lorenz-

Meutzner cycle with a bistable solenoid valve provides the desired level of temper-
ature control in the compartments. They also reported that an energy penalty of 6%
resulted due to the addition of the control valve and the resulting refrigerant charge
increase of 17% over the optimized baseline unit. These are 17% net savings over
a system with pure refrigerants.
REFERENCES
Ashley, C., 1945, U.S. Patent No. 2492725.
Dmitriev, W. et al., 1974, “Comparative Tests of Hermetic Compressor FR-O.15 on R12 and
Non-azeotropic Mixture of R12/R143,” Cholodilnaja Technika, Vol. 51, No. 6, pp.
25–27.
Jung, D.S. and R. Radermacher, 1991, “Simulation of a Single-Evaporator Refrigerator,”
International Journal of Refrigeration, Vol. 14, pp. 223–232.
Kuijpers, L.J.M., J.A. de Wit, A.A.J. Benschop and M.J.P. Janssen, 1990, “Experimental
Investigations into the Ternary Blend HCFC-22/124/152A as a Substitute in Domestic
Refrigeration,” IIR Purdue Refrigeration Conference.
Liu, Z., I. Haider, and R. Radermacher, 1995, “Simulation and Test Results of Hydrocarbon
Mixtures in a Modified-Lorenz-Meutzner Cycle Domestic Refrigerator,” HVAC&R
Research, Vol. 1, No. 2, pp. 127–142.
Lorenz, A. and K. Meutzner, 1975, “On application of non-azeotropic two component refrig-
erants in domestic refrigerators and home freezers,” XIV International Congress of
Refrigeration, Moscow.
Phillipp, L., 1948, U.S. Patent No. 2483842.
Radermacher, R. and D.S. Jung, 1992, “Refrigeration System,” U.S. Patent No. 5,092,138.
Radermacher, R. and D.S. Jung, 1993a, “Refrigerator System for Two-Compartment Cooling,”
U.S. Patent No. 5,235,820.
Radermacher, R. and D.S. Jung, 1993b, “Subcooling System for Refrigeration Cycle,” U.S.
Patent No. 5,243,837.
Radermacher, R., H. Ross and D.A. Didion, 1983, “Experimental Determination of Forced
Convection Evaporative Heat Transfer Coefficients for Non-Azeotropic Refrigerant
Mixtures,” ASME Winter Annual Meeting, Boston, MA, Paper No 83-WA/HT-54,
Nov., pp. 13–18.
Radermacher, R., K. Kim, W. Kopko and J. Pannock, 1995, U.S. Patent No. 5,406,805.
Rose, B., D.S. Jung and R. Radermacher, 1992, “Testing of Domestic Two-evaporator Refrig-
erators with Zeotropic Refrigerant Mixtures,” ASHRAE Transactions, Vol. 98, Pt. 2,
pp. 216–226.
Sand, J.R., E.A. Vineyard and V.D. Baxter, 1993, “Laboratory Evaluation of An Ozone-Safe
Nonazeotropic Refrigerant Mixture in a Lorenz-Meutzner Refrigerator Freezer
Design,” ASHRAE Transactions, Vol. 93, Pt. 1, pp. 1467–1481.
Schubert, A. and Herrick, C., 1964, U.S. Patent No. 3,019,614.
Stoecker, W.F. and D.J. Walukas, 1981, “Conserving Energy in Domestic Refrigerators
through the Use of Refrigerant Mixtures,” International Journal of Refrigeration,
Vol. 4, pp. 201–208.
Tiedemann, T., M. Kauffeld, K. Beermann and H. Kruse, 1991, “Evaluation of ozone-safe,
low greenhouse warming potential zeotropic refrigerant mixtures in household refrig-
erators/freezers,” XVIIIth International Congress of Refrigeration, Montreal, Canada.
Tiedemann, T. and H. Kruse, 1994, “Evaluation of zeotropic hydrocarbon mixtures in a

Lorenz-Meutzner-cycle refrigerator-freezer,” New Applications of Natural Working
Fluids in Refrigeration and Air Conditioning, IIR Conference, Hannover, Germany.
Vineyard, E.A., J.R. Sand and W.A. Miller, 1989, “Refrigerator-Freezer Energy Testing with
Alternative Refrigerants,” ASHRAE Transactions, Vol. 95, Pt. 2, pp. 295–299.
Vineyard, E.A., L. Roke and F. Hallett, 1991, “Overview of CFC Replacement Issues for
Household Refrigeration,” Proceedings of 1991 International CFC and Halon Alter-
native Conference, Washington D.C., pp. 310–316.
Zhou, Q., J. Pannock and R. Radermacher, 1994, “Development and Testing of a High
Efficiency Refrigerator,” ASHRAE Transactions, Vol. 100, Pt. 1, pp. 1351–1358.
Zhou, Q. and R. Radermacher, 1997, “Development of a Vapor Compression Cycle with a
Solution Circuit and Desorber/Absorber Heat Exchanger,” International Journal of
Refrigeration, Vol. 20, No. 2, pp. 85–95.
7 Refrigerant Mixtures in
Heat Pump Applications
Refrigerant mixtures were introduced for heat pump applications primarily to meet
environmental concerns. However, the use of refrigerant mixtures was considered
as early as the late 1800s and then again in the 1950s and thereafter to improve their
capacity control and energy efficiency. The use of mixtures was studied as alterna-
tives of hydrochlorofluorocarbons (HCFCs) after the inclusion of HCFCs as one of
controlled substances in the Montreal Protocol in 1992.
7.1 CAPACITY CONTROL

Heat pumps must be operated over the wide range of ambient temperatures. Fur-
thermore, the cooling and heating capacity of heat pumps tends to vary in opposition
to the load the heat pump is intended to match. The cooling capacity, for example,
decreases but the cooling load increases as the ambient temperature rises. The heating
capacity of the heat pump decreases but the heating load increases as the ambient
temperature drops. When the temperature difference between the ambient tempera-
ture and the desired conditioned space temperature is larger than the system design
condition, cooling or heating loads are larger than the cooling or heating capacity
of heat pumps. In this case, the capacity of the heat pumps is smaller than the cooling
or heating load though the heat pumps are operated with their full capacity. When
the temperature difference between the ambient temperature and the desired condi-
tioned temperature is smaller than the system design condition, cooling or heating
loads are smaller than the cooling or heating capacity of the heat pumps. In this
case, the heat pumps are only operated with partial capacity.
To operate the heat pumps with partial capacity, three general methods have
been utilized: cyclic operation, variable speed compressors using inverter control
and variable displacement compressors. Cyclic operation can have the disadvantage
of energy loss due to the excessive power consumption during the start up period.
Variable speed compressors have a disadvantage of higher cost and complexity of
system design, though they have an advantage of flexibility of control. Variable
displacement compressors are limited to automotive applications or to large systems
when individual cylinders are unloaded.
Refrigerant mixtures provide one more option for capacity control. If one com-
ponent of a mixture is separated from the circulating working fluid mixture and
stored selectively away from the cycle, the circulating mixture mass fraction is
affected by the amount of stored component. If a binary mixture of two pure
refrigerants with different boiling points is used, the mass fraction of the mixture
changes during its phase change process as explained in Chapter 2. Therefore, the
221
storage of one component by exploiting the mass fraction difference in the two-
phase state provides the opportunity to control the mixture mass fraction. Changes
of mixture mass fraction affect the density and latent heat of the circulating mixture,
resulting in capacity changes. Some options of capacity control by using refrigerant
mixtures are introduced here.
Using the method of modifying mixture mass fraction to adjust capacity is most
likely only suitable in a limited range around the ratio 1:2. Since the compressor
speed remains unchanged, the amount of work needed just to operate the compressor
(friction, oil pump and other sources) is essentially constant. Thus, during low
capacity operation, the fraction of lost work increases relative to compression work
done on the refrigerant and the overall system efficiency decreases.
7.1.1 ONE ACCUMULATOR CYCLE

Etherington et al. (1980) developed a variable capacity refrigeration cycle using an
accumulator with a special molecular sieve that is selectively reactive to a certain
refrigerant. As compared to the conventional refrigeration cycle with four basic
components (evaporator, condenser, compressor and expansion device), the one
accumulator cycle (OAC) has an additional accumulator as shown in Figure 7.1.1.
The accumulator is installed across the high and low pressure sides and connected
on one side to the condenser outlet before the expansion device and on the other
side to the compressor suction after the evaporator outlet. Both sides of the accu-
mulator can be shut off with valves C and D. Etherington et al. (1980) proposed
to use a molecular sieve that only absorbs R22 in the accumulator when the cycle
is charged with R12/R22.
3A 2'A
3
2'
Condenser
3I Receiver
Va lve C
Compressor
Heater
3II
Expansion
Device Evaporator Va lve D
4' 1
4'A 1A
FIGURE 7.1.1 One accumulator cycle.

Refrigerant Mixtures in Heat Pump Applications 223
Assume that a binary zeotropic mixture of R12 and R22 is charged in the cycle.
Normal boiling points of R12 and R22 are –29.8 and –40.8˚C, respectively, and R22
has a higher saturation pressure and larger latent heat than those of R12. For example,
the saturation pressures of R12 and R22 are 423 kPa and 681 kPa, respectively, at
10˚C saturation temperature. The latent heats of R12 and R22 are 148 kJ/kg-K and
196 kJ/kg-K, respectively, at 10˚C saturation temperature. Therefore, an R22-rich
mixture works at higher operating pressures and provides more capacity. When the
system capacity is larger than the load, there is a need for reducing capacity, so
valve C is opened and valve D is closed. Thus, R22 is selectively absorbed into the
molecular sieve. In this case, the R22 mass fraction of the circulating mixture
becomes lower than the originally charged mass fraction and the system capacity is
reduced due to the increase in R12 content. When the system capacity is smaller
than the load, there is a need for restoring system capacity, so valve C is closed and
valve D is opened. An electric heater helps to release the R22 that is absorbed in
the molecular sieve. In this case, the R22 mass fraction of circulating mixture
becomes the same as the originally charged mass fraction and the system capacity
is restored.
A similar effect can be achieved with a single accumulator located at the evap-
orator outlet only. Whenever a two-phase mixture leaves the evaporator, the liquid
phase is stored in the accumulator while the vapor continues to circulate through
the system. The stored liquid phase is rich in the high boiler (A) and the mass fraction
of the circulating mixture is shifted toward a higher content of the low boiler (B)
and the system capacity is increased.
Many air conditioners that also operate as heat pumps require a suction accu-
mulator to store excess charge during the heat pumping mode. Thus, this accumulator
causes a shift in mass fraction, increasing capacity during heating only. Using only
one accumulator causes a shift in mass fraction that is smaller than that possible
with the two accumulator configuration.
7.1.2 TWO ACCUMULATORS CYCLE

OAC uses a selectively reactive molecular sieve to control the mass fraction of
mixtures. Cycles introduced from here forward exploit the difference in boiling
points of mixture components. As compared to the OAC, the two accumulators cycle
(TAC) proposed by Vakil and Flock (1980) has one additional accumulator as shown
in Figure 7.1.2. One accumulator is installed on the high pressure side after the
condenser and the other accumulator is installed on the low pressure side after the
evaporator.
Assume that a binary zeotropic mixture of a low boiling point component (A)
and a high boiling point component (B) with mass fraction of x is charged in the
cycle. If the high pressure accumulator (receiver) is filled with a liquid mixture and
the low pressure accumulator is empty, the mass fraction of the liquid in the high
pressure accumulator is the same as the originally charged mass fraction x. Therefore,
the mass fraction of the circulating mixture remains the same as before and the low
pressure accumulator is almost empty and allows for superheating. If the situation
is reversed, the high pressure accumulator is empty and the low pressure accumulator
3A 2'A
Receiver
3
2'
Condenser
3I
Compressor
Expansion
Device
Evaporator Accumulator
4' 1
5
6
4'A 5A
FIGURE 7.1.2 Two accumulators cycle.
is filled with a liquid mixture and the low pressure accumulator stores a mixture
that is predominantly rich in component B because most of component A was already
released in the evaporator. Thus, the low pressure accumulator provides a mixture
rich in component A to the compressor and reduces the degree of superheating.
For example, Figures 7.1.3 and 7.1.4 show the saturated vapor density and latent
heat of condensation for the binary mixtures of R22/R114. Boiling points of R22
and R114 are –40.8 and 3.8˚C, respectively. Therefore, R22 works as component A
and R114 works as component B. These figures show the higher mass fraction of
30
80/20 wt.%
50/50 wt.%
25
20/80 wt.%
Density [kg/m3]
20
15
10
−10 −8 −6 −4 −2 0 2 4 6 8 10
Evaporating Temperature [°C]
FIGURE 7.1.3 Saturated vapor density of binary mixture (R22/R114).

170
80/20 wt.%
Latent Heat [kJ/kg] 160 50/50 wt.%
20/80 wt.%
150
140
130
120
40 42 44 46 48 50 52 54 56 58 60
Condensing Temperature [°C]
FIGURE 7.1.4 Latent heat of condensation for binary mixture (R22/R114).
R22 provides a higher saturated vapor density and latent heat of condensation at the
same temperature. Therefore, the first case of filled high pressure accumulator
provides smaller capacity due to the lower R22 mass fraction in the circulating
mixture. The second case of a filled low pressure accumulator provides a larger
capacity due to the higher R22 mass fraction in the circulating mixture. In this way,
the system capacity can be adjusted by the control of mixture mass fraction. Figure
7.1.5 shows the results of capacity modulation relative to the load variation.
nt
ref led
era
int f il
rig
po tor
ng la
Heating load System capacity

ili mu
bo ccu
Heating capacity
igh e a
n h sur
t
fri d
ran
re ille
h o res
ge
int r f
ric w p
po ato
Lo
ng ul
ili um
bo acc
ow er
n l ssu
h o re
ric gh p
Hi
New balance Balance Ambient

point point temperature
shifted to lower temperature
FIGURE 7.1.5 Results of capacity modulation (TAC).

3A 2'A
Receiver
7
3
2'
Condenser
Separator
8
3I
Compressor
Expansion
Device
Evaporator
Accumulator
4' 1
5
6
4'A 5A
FIGURE 7.1.6 Modified two accumulators cycle.
7.1.3 MODIFIED TWO ACCUMULATORS CYCLE

To increase the capacity change range, Vakil (1979) proposed a modified two accu-
mulators cycle (MTAC), as shown in Figure 7.1.6. In the MTAC, a separator replaces
the high pressure accumulator and is located at the condenser outlet. The high
pressure accumulator is located outside the cycle and in parallel with the separator.
Since the uncondensed vapor from the condenser is richer in component A and the
high pressure accumulator collects the liquid condensate, the mass fraction of A is
reduced in the circulating mixture. Therefore, MTAC provides a wider range of mass
fraction control than TAC. Vakil compared the capacity control ranges of these two
cycles as shown in Table 7.1. He showed that the capacity control of MTAC ranges
TABLE 7.1
Comparison of Capacity Control (R22/R114 with 50/50 mole%)
Minimum Minimum
Capacity Maximum for TAC for MTAC
Low accumulator Full Empty Empty

R22 composition in circulating mixture [mole%] 82.2 50.0 17.6
R22 composition in low accumulator liquid [mole%] 50 13 2.5
Evaporating pressure [MPa] 0.41 0.25 0.12
Condensing pressure [MPa] 1.60 1.04 0.60
Temperature glide during condensation [K] 7.0 17.8 15.1
Heating capacity [kW] 1.00 0.67 0.38
Source: Vakil, 1979.

8A
Sub-Condenser
8 7 3A 2'A
Parallel
Receiver 2'
9 Condenser
3
Receiver
Compressor
3I
Expansion
Device Evaporator Accumulator
4' 1
5
6
4'A 5A
FIGURE 7.1.7 Three accumulators cycle.
from 38 to 100% using an R22/R114 binary mixture (50/50 mol.%) and from 28 to
100% using an R23/R22/R114 ternary mixture (10/60/30 mol.%).
7.1.4 THREE ACCUMULATORS CYCLE

The disadvantage of MTAC is its slow capacity modulation compared to the ambient
temperature changes. To improve the capacity modulation speed, Vakil (1983) pro-
posed a three accumulators cycle (T3AC), as shown in Figure 7.1.7. In the T3AC,
a parallel accumulator is connected to the gas phase of the high pressure accumulator
and is located at the condenser outlet. The inlet to the parallel accumulator passes
through the subcondenser. Since the uncondensed vapor from the condenser is richer
in component A, the parallel accumulator can reduce the mass fraction of A in the
circulating mixture similar to the MTAC. However, T3AC can discharge the stored
liquid quickly with the help of the valve next to point 9 (Figure 7.1.7). Therefore,
T3AC can modulate its capacity faster than that of the MTAC.
7.1.5 CYCLE WITH RECTIFIER

As a third option to enhance the separation of a mixture, Schwind (1960) proposed
a cycle with rectifier (CWR), as shown in Figure 7.1.8. In this cycle, a rectifier is
installed between the condenser and expansion device. The condenser outlet is
connected to the overflow tank connected to the subcondenser (5), rectifier (7) and
rectifier heat exchanger (3I). A three-way valve is installed just before the expansion
valve and connected to the rectifier directly (3III) and rectifier heat exchanger (3II).
6A 5A 3A 2'A
Sub-Condenser
5 3
6 2'
7 Condenser
Rectifier
Overflow
Tank
3II 3I Compressor
3III
3-way
Valve
Heater Evaporator
1
3IV 4'
Expansion
Device
4'A 1A
FIGURE 7.1.8 Cycle with rectifier.
In normal operation, the three-way valve connects the rectifier heat exchanger
outlet (3III) and expansion valve inlet (3IV) as indicated by the dotted arrows. In
this case, the overflow tank delivers liquid refrigerant from the condenser into the
rectifier. The liquid refrigerant in the rectifier is fed into the expansion valve. Through
this process, the mass fraction of the mixture in the rectifier and that circulating in
the cycle becomes the same. If a large system capacity is required, the direction of
the three-way valve is reversed and the electric heater is turned on. The refrigerant
from the overflow tank (3II) is now connected to the expansion valve inlet (3IV).
The low boiling point refrigerant is then vaporized and fed into the subcondenser
where it is condensed again. This condensed low boiling point refrigerant enters the
overflow tank and is mixed with the circulating refrigerant. Through this process, the
mass fraction of low boiling point refrigerant in the circulating mixture increases and
the system capacity increases. Jakobs and Kruse (1978) examined this cycle option
with a binary mixture, R12/R114 (60/40 wt.%). They confirmed the circulating mass
fraction of R12 changed from 50 to 90% and achieved 30% more heating capacity.
7.1.6 MODIFIED CYCLE WITH RECTIFIER

The CWR concept was commercialized in Japan by Yoshida et al. (1989) and Figure
7.1.9 shows the CWR used. In this cycle, a rectifier and reservoir are installed parallel
to the expansion valve and connected by capillary tubes. The refrigerant from the
rectifier to the reservoir is cooled by the compressor suction gas. Yoshida et al. used
R13B1/R22 (30/70 wt.%) with boiling points of R13B1 and R22 of –57.8 and
–40.8˚C, respectively. During cooling (heating) at high (low) ambient temperature
operation, the expansion valve is normally closed with the refrigerant sent to the
reservoir. Vapor phase refrigerant rises in the rectifier and liquid from the reservoir
falls into the rectifier. These two streams encounter each other in the rectifier and
Auxiliary Condenser (reflex cooler)
8
9 Vapor Condenser
3 2'
Rectifier
3A 2'A
Compressor
10
Reservoir Capillary Expansion
Tube Device
Liquid Evaporator 1
Accumulator
4' 5 7
Capillary
Tube 6
4'A 5A
FIGURE 7.1.9 Modified cycle with rectifier.
exchange heat and mass. The high boiling point refrigerant in the rising vapor (R22)
is then condensed and leaves the rectifier with the liquid stream of the rectifier’s
lower end. The low boiling point refrigerant in the falling liquid (R13B1) is vaporized
and rises. In this way, the low boiling point refrigerant is stored in the reservoir and
the high boiling point refrigerant is circulating in the cycle. Therefore, the system
capacity is reduced. When a large capacity is required, the expansion valve opens
and the stored low boiling point refrigerant is released from the reservoir and
circulates in the cycle, resulting in a large capacity.
7.1.7 CYCLE WITH RECTIFIER-ACCUMULATOR

Rothfleisch (1995) combined the advantages of accumulator and rectifier and devel-
oped a cycle with a rectifier/accumulator (CRA), where Figure 7.1.10 shows the
schematic. The rectifier/accumulator is installed between the evaporator outlet and
compressor inlet and evaporator outlet and compressor inlet are connected to the top
of the rectifier/accumulator. The bottom end of the rectifier is connected to the
accumulator and a heater is installed in the liquid portion of the accumulator. The
major difference of the CRA compared to the CWR is the location of the rectifier.
The CWR has a rectifier on the high pressure side after the condenser, whereas the
CRA has a rectifier on the low pressure side in the suction accumulator.
Assume a binary mixture, R32/R134a, is charged. If the heater is not in operation,
the mixture is in thermal equilibrium. In this case, the rectifier/accumulator works
as a conventional accumulator. If the heater is turned on, the accumulator liquid
reservoir temperature is higher than the rectifier and the refrigerant from the evap-
orator continues to flow through the head of the rectifier. Vapor phase refrigerant
from the accumulator also rises in the rectifier and liquid from the top portion of
3A 2'A
3
2'
Condenser
Device
1
Evaporator
4'
5
4'A 5A Rectifier
Accumulator
Heater
FIGURE 7.1.10 Cycle with rectifier accumulator.
the rectifier that was not released in the evaporator drops through the rectifier to the
accumulator. These two streams encounter each other in the rectifier and exchange
heat and mass. The high boiling point refrigerant in the rising vapor (R134a) is then
condensed and leaves with the liquid. The low boiling point refrigerant in the falling
liquid (R32) is vaporized and rises with the vapor. In this way, the high boiling point
refrigerant (R134a) is stored in the accumulator and the low boiling point refrigerant
(R32) is circulating in the cycle. The advantage of the CRA compared to the cycle
with an accumulator only is a reduction in the size of the accumulator. Moreover,
CRA is able to extend the composition change by eliminating the thermal equilibrium
constraint.
Rothfleisch (1995) investigated the performance of the CRA with a binary
mixture, R32/R134a (30/70 wt.%), and a ternary mixture, R32/R125/R134a (23/25/52
wt.%). He confirmed that the maximum mass fraction shift of the circulating mixture
amounts to 54/46 wt.% for R32/R134a and 36/36/28 wt.% for R32/R125/R134a.
He also found that the heating seasonal performance factor was improved by about
3% with the CRA in use.
7.2 R22 REPLACEMENT

7.2.1 SCREEN OF REFRIGERANT MIXTURES
Systematic screening approaches have been conducted to select potential refrigerant
mixtures to substitute R22. Vineyard et al. (1989) applied two selecting criteria —
hard criteria and soft criteria — to more than 200 pure compounds that would make
up the components of zeotropic mixtures. Hard criteria (toxicity, instability and
TABLE 7.2
Performance Comparison of Pure Refrigerants Investigated by ORNL
Cooling “A” Cooling “B” Heating “47S” Heating “17L”
Capacity Capacity Capacity Capacity
Refrigerant [kW] COP [kW] COP [kW] COP [kW] COP
R32 17.3 2.6 20.3 3.0 15.5 3.1 8.2 2.4

R125 9.0 2.0 11.6 2.4 9.2 2.6 5.0 2.1
R143a 11.3 2.3 13.9 2.7 10.6 2.8 5.6 2.3
R22 10.1 2.6 11.8 3.0 9.6 3.0 4.7 2.4
R218 — — — — — — — —
R134a 6.5 2.5 7.8 2.9 5.9 2.9 2.7 2.3
R152a 6.4 2.7 7.5 3.1 5.7 3.0 2.7 2.5
R124 3.4 2.4 4.2 2.8 2.8 2.8 1.2 2.3
R124a — — — — — — — —
R142b 3.6 2.6 4.3 3.0 3.2 3.0 1.4 2.4
C318 2.7 2.2 3.4 2.6 2.5 2.6 1.1 2.1
R143 — — — — — — — —
Source: Vineyard et al., 1989.
ozone-depletion potential or ODP) were used to eliminate a refrigerant from con-

sideration. Soft criteria (flammability, boiling point and commercial availability)
were also used to eliminate a refrigerant but only as a flexible criteria. After applying
these two criteria, the following seven refrigerants remained: R125, R22, R218,
R134a, R124, R124a and C318. By relaxing the flammability criteria, five more
refrigerants were added: R32, R143a, R152a, R142b and R143.
To evaluate performance of these twelve refrigerants at ASHRAE cooling con-
ditions (A and B) and heating conditions (47S and 17L), the simple cycle program
developed by McLinden, Cycle 5A, was utilized. Results of the cycle performance
calculation are shown in Table 7.2. R218, R124a and R143 were excluded in the
calculation due to the availability of property routines. From Table 7.2, R125 and
C318 showed 10% lower COP than that of other refrigerants; thus, these two
refrigerants were eliminated from further evaluation. Once the performance potential
of pure refrigerants was evaluated, the temperature glide of the binary mixtures of
selected pure refrigerants was evaluated to discover mixtures that with the best
matching temperature glides with heat exchanging fluids. In this analysis, the mass
fraction of each component for each mixture was fixed at 50/50 wt.%. The temper-
ature glide of each mixture at 1102 kPa saturation pressure was then compared, as
shown in Table 7.3. The authors decided the temperature glides between 10 to 30°C
contained the most potential for better temperature matching in the heat exchangers,
as shown with the boldface values in Table 7.3. Moreover, only R32 and R143a
showed higher capacity than R22 from the cooling and heating capacity analysis
shown in Table 7.2. Finally, R32/R124, R32/R142b, R143a/R124, R143a/R142b and
R143a/C318 were selected as the best mixtures by combining the performance
results (Table 7.2) and the temperature glides (Table 7.3).
TABLE 7.3
Temperature Glides of Binary Mixtures for 50/50 wt.%
R32 3 3 4 4 8 8 23 23 23 28 44
R125 3 3 4 6 6 19 19 19 23 40
R143a 3 4 5 5 17 17 17 23 38
R22 3 4 4 11 11 11 15 29
R218 3 3 7 7 7 10 23
R134a 3 3 3 3 5 11
R152a 3 3 3 4 8
R124 3 3 3 4
R124a 3 3 4
R142b 3 4
C318 3
R143
Source: Vineyard et al., 1989.
flammable flammable
H
H
R50 R170
R160 R161
R40 R41
toxic toxic R150 R151 R152a
R30 R31 R32
R140a R141b R142b R143a
R20 R21 R22 R23 R130a R131 R132b R133a R134a
R120 R121 R122 R123 R124 R125

R10 R11 R12 R13 R14
R110 R111 R112 R113 R114 R115 R116
Cl F
Cl F
long atmospheric long atmospheric
lifetime lifetime
(a) Methane series (b) Ethane series
FIGURE 7.2.1 Systematization of properties (Pannock and Didion, 1991).
7.2.2 SCREEN OF HFC REFRIGERANT MIXTURES

Figure 7.2.1 shows methane- and ethane-based refrigerants arranged according to
molecular structure. Pure compounds with potential as R22 alternatives are shown
in Table 7.4. These six methane- and ethane-based refrigerants having zero ozone
depletion potential (ODP) are listed and evaluated based on similar boiling points,
flammability and being environmentally benign (Pannock and Didion, 1991).
Unfortunately, none of the above refrigerants satisfies all these requirements.
Thus, the mixing of these refrigerants was suggested to obtain the desired properties.
In 1991, the Air-conditioning and Refrigeration Institute (ARI) started the Alternative
TABLE 7.4
Characteristics of Potential Pure Component
Refrigerant Characteristics Normal Boiling Point [˚C]
R22 Base fluid –40.8

R23 Critical temperature is too low –82.0
R32 Flammable, too high volumetric capacity –51.7
R125 High DGWP, low theoretical efficiency –48.1
R143a Flammable, high DGWP –47.2
R134a Low volumetric capacity –26.1
R152a Flammable –24.0
DEWP = direct global warming potential.
Refrigerants Evaluation Program (AREP) to find and evaluate promising alternatives

to the refrigerants R22 and R502 for products such as unitary air conditioners, heat
pumps, chillers, refrigeration equipment and ice-making machines (Godwin, 1993).
This test program involved researchers worldwide and shared experimental results.
AREP investigated 16 refrigerants for R22 replacements and six refrigerants for
R502 replacements, as shown in Tables 7.5 and 7.6. Though no single alternative
refrigerant is chosen as a universal replacement to R22, experimental results for
some interesting refrigerants show a similar cooling and heating performance as
R22, as shown in Table 7.7.
After years of research, three potential refrigerant mixture candidates for R22
replacements have emerged: R134a, R407C and R410A. R134a has a lower vapor
pressure than R22 and results in a lower volumetric capacity. R407C has a vapor
pressure similar to R22 and performs within a 6% variation. R410A has a 50%
higher vapor pressure and has shown better performance within 10% variation
compared to R22. In terms of vapor pressure, R407C appears to be an “easy-to-
TABLE 7.5
R22 Alternative Refrigerants Investigated by AREP
Type Refrigerant
Pure refrigerant R134a

R290
R717
Binary mixture R32/R125 (60/40; 50/50 wt.%)
R32/R134a (20/80; 25/75; 30/70; 40/60 wt.%)
R125/R143a (45/55 wt.%)
Ternary mixture R32/R125/R134a (10/70/20; 23/25/52; 24/16/60; 25/20/55; 30/10/60 wt.%)
Quaternary mixture R32/R125/R290/R134a (20/55/5/20 wt.%)
Source: Godwin, 1993.

TABLE 7.6
Type Refrigerant
Binary mixture R125/R143a (45/55; 50/50 wt.%)

R32/R125/R134a (10/70/20; 20/40/40 wt.%)
Ternary mixture R32/R125/R143a (10/45/55 wt.%)
R125/R143A/R134a (44/52/4 wt.%)
TABLE 7.7
Cooling Cooling Heating Heating
Refrigerant Capacity Efficiency Capacity Efficiency
R32/R125 (60/40 wt.%) –3 to +7% –10 to +5% –3 to +4% –3 to +1%

R32/R125 (50/50 wt.%) –2 to +5% +1 to +6% n/a n/a
R32/R125/R134a (30/10/60 wt.%) –5 to +5% –10 to +2% –4 to +5% –13 to 0%
R32/R125/R134a (23/25/52 wt.%) –7 to +1% –10 to –3% –2 to +2% –7 to +2%
implement” substitute whereas R410A appears to be a “difficult-to-implement”

substitute requiring major system redesign. R410A seems to be the leading long-
term candidate for the new residential and light commerce equipment (Chin and
Spatz, 1999).
By using the Mark V DOE/ORNL heat pump model, Chin and Spatz (1999)
also noted that the performance of R410A is higher than R22 only when the ambient
temperature is lower than 35˚C due to the compressor efficiency degradation at the
higher ambient temperature, as shown on Figures 7.2.2 and 7.2.3.
14
R22
13
R410A
12
Capacity [kW]
11
10
8
28 35 46 52 57
Ambient Temperaure [°C]
FIGURE 7.2.2 Ambient temperature vs. performance changes (Chin and Spatz, 1999).
4.5
R22 (Chin)
4.0 R410A (Chin)
R22 (Fluor)
3.5 R410A (Flour)
3.0
COP
2.5
2.0
1.5
1.0
25 30 35 40 45 50 55 60
Ambient Temperaure [°C]
FIGURE 7.2.3 Ambient temperature vs. performance changes (Chin and Spatz, 1999).
REFERENCES
Chen, J. and H. Kruse, 1997, “Mass Fraction Shift Simulation for the Mixed Refrigerants
R404A, R32/R134A, and R407C in an Air-conditioning System,” International Jour-
nal of HVAC&R Research, Vol. 3, No. 2, pp. 149–157.
Chin, L. and M. W. Spatz, 1999, “Issues Relating to the Adoption of R410A in Air Condi-
tioning Systems,” Proceedings of 20th International Congress of Refrigeration,
IIR/IIF, No. 179.
David, G. and M. Menzer, 1993, “Results of Compressor Calorimeter Tests in ARI’s R22
Alternative Refrigerants Evaluation Program,” Proceedings of ASHRAE/NIST Refrig-
erants Conference for R22/R502 Alternatives, pp. 1–18.
Fisher, S.K. and J.R. Sand, 1993, “Screening Analysis for Chlorine-Free Alternative Refrig-
erants to Replace R22 in Air-Conditioning Applications,” ASHRAE Transactions,
Vol. 99, Pt. 2, pp. 627–634.
Hughmark, G.A., 1962, “Holdup in Gas-Liquid Flow,” Chemical Engineering Progress,

Vol. 58, No. 4, pp. 62–65.
Jacobs, R. and H. Kruse, 1978, “The Use of Nonazeotropic Refrigerant Mixtures in Heat
Pumps for Energy Saving,” Proceedings of Meeting of Commission B2 of Interna-
tional Institute of Refrigeration.
Rothfleisch, P.I., 1995, “A Simple Method of Composition Shifting with a Distillation Column
for a Heat Pump Employing a Zeotropic Refrigerant Mixture,” NIST Report, NISTIR
5689.
Smith, S.L., 1969, “Void Fractions in Two-Phase Flow: A Correlation Based upon an Equal
Velocity Head Model,” Proceedings of the Institute of Mechanical Engineers 184,
Pt. 1, No. 36, pp. 647–664.
Vakil, H.B., 1981, “Means and Method for Independently Controlling Vapor Compression
Cycle Device Evaporator Superheat and Thermal Transfer Capacity,” U.S. Patent No.
4,290,272.
Vakil, H.B., 1983, “Means and Method for Modulating and Controlling the Capacity of a
Vapor Compression Cycle Device,” U.S. Patent No. 4,384,460.
Vakil, H.B., 1983, “New Concept in Capacity Modulation using Nonazeotropic Mixtures,”
General Electric Report No. 83CRD212.
Vakil, H.B., 1979, “Vapor Compression Cycle Device with Multi Component Working Fluid
Mixture and Method of Modulating Its Capacity,” U.S. Patent No. 4,179,898.
Vakil, H.B. and J.W. Flock, 1980, “Vapor Compression Cycle Device with Multi Component
Working Fluid Mixture and Method of Modulating Its Capacity,” U.S. Patent No.
4,217,760.
Vineyard, E.A, J.R. Sand and T.G. Statt, 1989, “Selection of Ozone-Safe, Nonazeotropic
Refrigerant Mixtures for Capacity Modulation in Residential Heat Pump,” ASHRAE
Transactions, Vol. 95, Pt.1, pp. 34–46.
Yoshida, Y., S. Suzuki, Y. Mukai, K. Nakatani and K. Fujiwara, 1989, “Development of
Rectifying Circuit with Mixed Refrigerants,” International Journal of Refrigeration,
Vol. 12, pp. 182–187.
8 Heat Transfer of
Refrigerant Mixtures
In this chapter, the heat transfer characteristics of refrigerant mixtures are discussed,
including evaporation and condensation. The single-phase heat transfer of mixtures
is affected only to the degree that the transport properties change. As can be expected
from the phase equilibrium characteristics of mixtures, the heat transfer behavior of
mixtures in the two-phase range is quite different from that of pure refrigerants. In
this chapter, the various features of the heat transfer of mixtures are described and
recent efforts of heat transfer measurements and the development of correlations are
summarized.
8.1 NUCLEATE POOL BOILING HEAT

TRANSFER COEFFICIENTS
The pool boiling behavior of zeotropic mixtures is somewhat different from pure
refrigerants, as shown in Figure 8.1.1. Due to the difference in vapor and liquid
mass fractions of the zeotropic mixture, the onset of boiling requires a higher wall
superheating than that of a pure fluid. The critical heat flux for mixtures can be
either higher or lower than that of pure fluids.
The measured pool boiling heat transfer coefficient of the zeotropic mixture is
lower than that of the ideal pool boiling heat transfer coefficient predicted from that
of pure fluids. Figure 8.1.2 shows the pool boiling heat transfer coefficient of
R11/R113 mixtures on the outside surface of three different tubes at a pressure of
1 bar. The ideal heat transfer coefficient of zeotropic mixtures is defined here as the
line connecting the two heat transfer coefficients of pure fluids, shown as a thick
solid line in Figure 8.1.2 (Trewin et al., 1994). The heat transfer coefficient of
zeotropic mixtures does not change linearly with mass fraction but it shows degra-
dation compared to the ideal heat transfer coefficient. Moreover, the heat transfer
coefficient of zeotropic mixtures shows much higher degradation in enhanced tubes.
To understand this behavior of zeotropic mixtures, the processes that lead to the
growth of a bubble must be considered.
Figure 8.1.3 explains the bubble growth mechanism in zeotropic mixtures. Since
the mass fraction of the vapor inside the bubble is markedly different than that of
the surrounding liquid — as discussed in Chapter 2 — the more volatile component
must diffuse through the liquid to the growing bubble. The liquid layer immediately
surrounding the bubble becomes depleted of the more volatile component and forms
a diffusion area around the bubble. In order for the bubble to grow further, the more
volatile component must diffuse through this layer of depleted liquid. The driving
force is the superheating. The effective superheating of the liquid layer surrounding
237
Pure Liquid
Binary Mixture
Film
Boiling
Critical
Heat Flux
Minimum
Surface Heat Flux Heat Flux
Onset of
Nucleate
Boiling
Wall Superheat
FIGURE 8.1.1 Schematic diagram of pool boiling curve for binary mixture.
Heat Transfer Coefficient [kW/m2-K]
30
Plain tube
25 Turbo-B
High flux
Ideal HTC
20
15
10
0
0 0.25 0.5 0.75 1.0
R11 Mass Fraction
P = 1 bar q = 30 kW/m2
FIGURE 8.1.2 Pool boiling heat transfer coefficients of R11/R113 mixtures (Trewin et al.,
1994).
the bubble is no more than the temperature difference between the wall temperature
and the bulk liquid saturation temperature for the given overall mass fraction. Since
the liquid layer surrounding the bubble is enriched in the low vapor pressure com-
ponent, its saturation temperature is higher than that of the bulk liquid. This reduction
of the effective superheating is the main and most complex contribution to the heat
transfer coefficient degradation.
The reasons for the heat transfer coefficient degradation of zeotropic mixtures
is summarized as follows:
Heat Transfer of Refrigerant Mixtures 239
Bubble Liquid
Surrounding
Bubble
R
Diffusion
Area
Superheating Tsv Ttp
Ttp Tsl
Radius
FIGURE 8.1.3 Bubble growth mechanism.
• Increase of the local saturation temperature because the more volatile

component evaporates more readily than the other component during the
bubble growth process as explained above (Van Wijk et al., 1956).
• Additional mass diffusion resistance of the more volatile component in
the bubble (Sterning and Tichacek, 1961).
• Large changes of mixture physical properties with mass fraction (Stephan
and Preusser, 1979).
• Lower boiling site densities caused by higher wall superheating (Grigor’ev,
1962).
• Retardation of the main heat transport mechanisms (Thome, 1983).
• Degradation of transport properties for mixtures as compared to pure
components.
Since hydrofluorocarbons (HFCs) and their mixtures were introduced, research

on nucleate pool boiling of these refrigerants has been conducted on plain tubes,
low-finned tubes and enhanced tubes as summarized in Table 8.1 (Thome, 1996).
Ohata and Fujita (1994) showed the degradation of mixture heat transfer coef-
ficients. Trewin et al. (1994) compared mixture heat transfer coefficients in three
different tubes, as shown in Figure 8.1.2. Buschmeier et al. (1994), Schmidt (1995)
and Gorenflo et al. (1995) investigated the heat transfer coefficients of the flammable
refrigerant mixtures such as propane, butane and ethane.
8.2 FLOW BOILING HEAT TRANSFER COEFFICIENTS

Pool boiling relies on one major mechanism: bubbles are formed at a heated surface
then detach and rise through an essentially stagnant pool to the surface. In flow
TABLE 8.1
Nucleate Pool Boiling Research
Authors Refrigerant Psat or Tsat Test Surface Oil [%]
Webb and Pais R123, R134a, R11, R12, 27˚C PT, FT, TB, SE None
(1991) R22, R123
Gorenflo and Sokol R134a 1.4–36.5 bar PT, FT, TX None
(1991) R227 1.0–26.4 bar
Shi and Hahne R134a 2.0–25.0 bar 0.1 mm wire None
(1991) R152a 2.2–23.0 bar
Webb and Pais R123, R134a, R11, R12, 4.4 and 26.7˚C PT, FT, TB, TX, None
(1992) R22 SE
Gupte and Webb R123, R11 4.4 and 26.7˚C SE None
(1992)
Memory et al. R114 2.2˚C PT, FT, TB, HF 0–10
(1993)
Webb and McQuade R123, R11 4.4˚C PT, TB, SE 0–5
(1993)
Muller et al. (1993) R134a 4.4 and 32˚C 0.1 mm wire 0–10
2.0 mm strip
Gupte and Webb R123 4.4 and 26.7˚C TB, SE None
(1994) R134a SE
R11 FT, TB, SE
Schomann et al. Propane 0.7–17.1 bar PT None
(1994) R114 2.3–29.3 bar
Buschmeier at al. Propane/n-butane 3.8–21.1 bar PT None
(1994)
Ohta and Fujita R11/R113 1.0–15.0 bar Flat plate None
(1994)
Trewin at al. (1994) R11/R113 1.03 bar PT, TB, HF None
Schmidt (1995) R22/R142b 0.05–0.20a Flat disk None
Propane/n-butane 0.03–0.90a
Ethane/n-butane 0.10–0.60a
Gorenflo et al. Propane/i-butane/n-butane 1.6–12.6 bar PT None
(1995)
Palm (1995) R134a 0 and 20˚C PT, FT, TB, TX 0–3
R22 0 and 25˚C and Sevac
Note: PT: Plain tube, FT: Low-finned tube, TB: Turbo B tube, TX: Gewa TX 19 tube, SE: Gewa SE
tube, HF: High flux,
a Reduced pressure.
Source: Thome, 1996.
boiling, the mechanism is more complex. Depending on flow conditions, there is

still a significant boiling contribution but also a second one — evaporation. Whenever
the tube is mostly filled with liquid or the film thickness of the liquid on the wall
is high, the boiling contribution often dominates the heat transfer. As the vapor
quality increases and the liquid film thickness is diminished, evaporation of molecules
from the liquid surface becomes a more important contribution. When the liquid
film becomes thinner than the diameter of a bubble before it detaches, the evaporation
process dominates (suppression of nucleate boiling). Most flow boiling correlations
try to tie these two contributions to the heat transfer process by having a boiling
term and an evaporation term. The fact that the mass fraction of liquid and vapor
phases are quite different for zeotropic mixtures affects these heat transfer processes
quite significantly and must be accounted for in the correlations as well. Table 8.2
summarizes research on flow boiling heat transfer coefficients of mixtures based on
Wang and Chato’s (1995) summary, Thome’s (1996) summary and an additional
survey of the latest literature.
Ross et al. (1987) investigated convective boiling heat transfer coefficient of
R152a/R13B1. Their results can be summarized as follows:
• Full suppression of nucleate boiling of pure fluids occurs only at low

pressures.
• Mixtures can reach full suppression of nucleate boiling easier than pure
fluids due to the mass transfer resistance.
• The heat transfer coefficients of mixtures are severely degraded (up to
50%) compared to pure fluids.
• For the evaporation dominated heat transfer regime, Chen’s correlation
applies well for both pure fluids and mixtures with a Prandtl number
correction for pure fluids and without correction for mixtures. This means
there is some nucleation for pure fluids while nucleate boiling is sup-
pressed for mixtures.
• For the nucleate boiling dominated heat transfer regime, Stephan and
Abdelsalam’s (1981) correlation works well (within 20%) for pure fluids
and Thome’s (1983) correlation for mixtures.
• For the mixtures, there is a circumferential variation of the heat transfer
coefficient opposite that found for pure fluids. This phenomenon means
that there is a circumferential gradient in mass fraction and interfacial
temperature.
Jung et al. (1989a,b) investigated the convective boiling heat transfer coefficient
of R22/R114 and R12/R152a. Their results are summarized here:
• Flow boiling characteristics of zeotropic mixtures are different from those

of azeotropic mixtures that behave similar to the pure fluids. Zeotropic
mixtures have a mass diffusion effect due to the boiling temperature
difference between the constituents.
• Flow boiling heat transfer coefficients of mixtures are lower than the ideal
heat transfer coefficient based on the mixing rule for heat transfer coef-
ficients of pure fluids for nucleate pool boiling (Figure 8.2.1). The actual
mixture heat transfer coefficient at 65% quality was lower by 19, 36 and
35% than that of ideal values for the R22 compositions of 0.23, 0.47 and
0.77, respectively. Up to 80% of this heat transfer coefficient degradation
is estimated to be due to the physical property variation. The mass transfer
TABLE 8.2
In-tube Flow Boiling Research
Mass Flux
Authors Refrigerant [kg/m2-s] Tube/ID [mm]
Singal et al. (1983) R12/R13 n/a Plain/9.5

Radermacher et al. (1983) R13B1/R152a n/a Plain/9.1
Ross et al. (1987) R13B1/R152a n/a Plain/9.1
Mulroy et al. (1988) R22/R114, R13/R12 n/a Annuli and ID Fins
Jung et al. (1989a, 1989b) R22/R114, R12/R152a 250–720 Plain/9.1
Jung and Radermacher (1989) R22/R114, R12/R152a 250–720 Plain/9.1
Hiraha et al. (1989) R12/R22, R22/R114 100–350 Plain/8.0
Conklin and Vineyard (1990) R143a/R124 150–350 Fluted/16.9
R143a/R124 160–460 Finned/15.3
Murata and Hashizume (1990) R11/R114 100–300 Plain/10.3
Eckels and Pate (1991b) R22/R152a/R124 135–360 Plain/8.0
Sami and Duong (1991, 1992) R22/R114 180–290 Fluted annuli/28.6
and 32.3
Sami and Schnotale (1992) R22/R114, R22/R152a 142–255 Fluted/21.2
Sami et al. (1992) R22/R152a/R114, 142–255 Fluted/21.2
R22/R152a/R124
Niederkruger et al. (1992) R846/R12 80–400 Plain/14.0
Doerr and Pate (1993) R32/R134a 100–400 Plain/8.0
R32/R125/R134a 125–360
Torikoshi and Ebisu (1993) R32/R134a 100–400 Plain/8.7
Torikoshi and Ebisu (1993) R32/R125 100–400 Plain/N/a
Wattelet et al. (1993) R32/R125 n/a Plain/7.7
Murata and Hashizume (1993) R123/R134a 100–300 Plain/10.3
Microfin/10.7
Wattelet et al. (1994a) R22/R124/R152a 25–100 Plain/7.04
Kattan at al. (1994) R502 100–300 Plain/12.0
R125/R290/R22 102–318
R125/R143a/R134a 102–320
Rohlin (1994) R22/R142b, R32/R134a 30–160 Plain/15.0
Bivens and Yokozeki (1994) R32/R134a, 200 Plain/8.0
R32/R125/R134a
Melin and Vamling (1995) R22/R142b, Propane/n- 85–316 Plain/10.0
butane
Goto et al. (1995) R32/R125 80–433 Microfin/6.4 and 9.5
R32/R125/R134a 100–365
Wijaya and Spatz (1995) R32/R125 160–561 Plain/7.8
Uchida et al. (1996) R32/R125/R134a 100–500 Plain, Microfin/6.4
Sundaresan et al. (1996) R32/R125, R32/R125/R134a 125–375 Plain, Microfin/9.5
Shin et al. (1997) R32/R134a, R32/125 424–741 Plain/7.7
R290/R600a 265–583
Note: ID: Inside diameter, OD: Outside diameter.
Sources: Wang and Chato, 1995; Thome, 1996.

Heat Transfer Coefficient [kW/m2-K]

7
xq = 0.35
xq = 0.50
6 xq = 0.65
Ideal mixture HTC
5
2
0.0 0.2 0.4 0.6 0.8 1.0
R22 Mass Fraction
m=23 g/sq = 17 kW/m2
FIGURE 8.2.1 In-tube boiling heat transfer coefficients of R22/R114 mixtures (Jung et al.,
1989a,b).
resistance is estimated to contribute less than 20% of the heat transfer

coefficient degradation.
• Flow boiling heat transfer coefficients of mixtures are a function of the
mixture mass fraction, vapor quality and heat flux (Figure 8.2.2). A steep
gradient near pure R22 is due to the physical property variation. When
the vapor quality is less than 20 to 30%, the nucleate boiling contribution
is dominant; therefore, the heat transfer coefficient increases as the heat
flux increases in this partial boiling regime. In the partial boiling regime,
both the nucleate and convective boiling contribute. Moreover, the heat
transfer coefficient decreases due to the reduction of the nucleate boiling
contribution as the vapor quality increases.
Liquid layer
Heat Transfer Coefficient, HTCtp
q5
Va por core
Increasing heat flux
q4 Bubble
hnbc
q3
hcec
q2
hcec
q1
hnbc : nucleate boiling contribution

hcec : convective evaporation contribution
Quality
FIGURE 8.2.2 Boiling heat transfer mechanisms (Jung et al., 1989a,b).

• However, convective boiling is dominant when the vapor quality is high. For
the convective boiling regime, the heat transfer coefficient is not affected
by the heat flux since the nucleate boiling is suppressed (Figure 8.2.2).
• The mixture shows a different circumferential variation in wall tempera-
ture and heat transfer coefficient from that of pure fluids. Due to gravity,
the liquid film thickness at the top is thinner than that at the bottom
(assuming a constant heat flux). Therefore, for pure fluids, the top part
has better heat transfer than the bottom part due to reduced heat transfer
resistance. This heat transfer variation results in a lower wall temperature
at the top than at the bottom. However, this film thickness variation causes
a mass fraction variation for zeotropic mixtures. Due to the thinner film
thickness at the top, the mass fraction of the more volatile component in
the top film portion is reduced and causes a heat transfer coefficient
reduction due to an increased mass transfer resistance. Therefore, the
bottom portion of the liquid film provides better heat transfer than the top
portion for zeotropic mixtures. This heat transfer variation results in a
lower wall temperature at the bottom than at the top.
Shin et al. (1997) investigated convective boiling heat transfer coefficient of

R32/R134a (25/75 wt.%), R290/R600a and R32/R125 (50/50 wt.%). Their results are:
• Similar to Jung et al.’s (1989) results, the heat transfer coefficient increases
as the heat flux increases in this partial boiling regime and the heat transfer
coefficient is not affected by the heat flux for the convective boiling regime.
• The heat transfer coefficient increases when the quality is higher than
20% as the refrigerant mass flux increases due to the increased mean
velocity of the refrigerant.
• Similar to Jung et al.’s (1989) results, the local heat transfer coefficient of
the zeotropic mixture at the top is lower than that at the bottom. However,
the local heat transfer coefficient of the azeotropic mixture at the top is
higher than that at the bottom as is the case for pure fluids.
Many other investigators confirmed the boiling heat transfer coefficient degra-
dation as compared to the ideal heat transfer coefficient as follows:
• Torikoshi and Ebisu (1993) studied the boiling heat transfer coefficient
of R32/R134a (30/70 wt.%) and reported the degradation of the boiling
heat transfer coefficient as compared to the ideal boiling heat transfer
coefficient was 30 and 20%, respectively, for the mass flux of 91 kg/m2-s
and 182 kg/m2-s when the saturation temperature was 0ºC.
• Rohlin (1994) reported the degradation of the boiling heat transfer coef-
ficient of R22/R142b (60/40 wt.%) as 40% when the saturation temper-
ature was 0˚C.
Some researchers investigated the boiling heat transfer coefficient of binary and
ternary mixtures that are considered as replacements of existing pure refrigerants,
R12 and R22:
• Sami et al. (1992) studied the boiling heat transfer coefficient of

R22/R152a/R114 (53/19/28 wt.%) and R22/R152a/R124 (50/20/30 wt.%)
in an enhanced tube and reported the boiling heat transfer coefficient of
these two ternary mixtures is lower than R22 and higher than R12. The
boiling heat transfer coefficient of R22/R152a/R124 is higher than that
of R22/R152a/R114 (53/19/28 wt.%) because the heat transfer coefficient
of R124 is better than that of R114.
• Wattelet et al. (1994a) studied the boiling heat transfer coefficient of
R22/R124/R152a (52/33/15 wt.%) and compared it with that of R12 and
R134a. For an annular flow (mass flux: 200–500 kg/m2-s, heat flux:
5–30 kW/m2), the mixture has a heat transfer coefficient similar to R134a
and 10% higher heat transfer coefficient than that of R12. When the heat
flux is low, its nucleate boiling is more suppressed than R134a or R12.
For a stratified flow (mass flux: 25–100 kg/m2-s, heat flux: 2–10 kW/m2),
the mixture has a heat transfer coefficient similar to R134a. As the mass
flux decreases, the heat transfer coefficients of the mixture are much lower
than R12.
• Wijaya and Spatz (1995) reported that the boiling heat transfer coefficient
of R410A is much higher (42 to 63%) than that of R22.
• Uchida et al. (1996) studied the boiling heat transfer coefficient of
R32/R125/R134a (30/10/60 wt.%) and R22 inside horizontal tubes with
smooth, grooved and cross-grooved inner surfaces. They found that the
cross-grooved tube has the highest heat transfer coefficient with a mixture
nearly three times higher than that of the smooth tube and 20 to 40%
higher than that of the grooved tube. However, the heat transfer coefficient
of R22 in the cross-grooved tube is lower than that of the grooved tube.
They attributed this difference to the stirring effect of the liquid phase by
the notches that reduce the composition variation in the liquid phase of
the mixture.
• Sundaresan et al. (1996) reported their comparisons of the boiling heat
transfer coefficients of R22, R410A and R407C in a smooth tube and
microfin tube. They found that the heat transfer coefficients of R410A are
the highest. The heat transfer coefficients of R410A is 25% higher than
R22 and 72% higher than R407C in the smooth tube; the heat transfer
coefficients of R410A is 29% higher than R22 and 100% higher than
R407C in the smooth tube.
8.3 CORRELATIONS FOR FLOW BOILING HEAT TRANSFER

For modeling purposes, accurate heat transfer correlations for mixtures are needed
to properly design heat exchangers. This section presents literature survey results of
flow boiling heat transfer correlations.
A considerable number of heat transfer correlations of flow boiling for pure
fluids have been proposed. However, only a few correlations are published for
mixtures. The applicability of these general correlations for mixtures must be proven.
Two review papers by Webb and Gupte (1992) and Darabi et al. (1995) offered a
summary of the most referenced correlations for flow boiling. Webb and Gupte
classified heat transfer models into three categories: superposition, enhancement and
asymptotic models. In this section, twelve nondimensional general correlations are
examined.
Chen, Bennett-Chen, Gungor-Winterton and Jung’s correlations utilize a super-
position model. In this model, the total heat transfer coefficient is the sum of nucleate
boiling and bulk convection contributions. Shah, Schrock-Grossman, Mishra, Sami
and Shin’s correlations utilize an enhancement model. In this model, the two-phase
heat transfer coefficient enhances the single-phase heat transfer coefficient of a
flowing liquid by a two-phase enhancement factor. Liu-Winterton, Wattelet and
Bivens-Yokozeki’s correlations utilize an asymptotic model. In this model, the total
heat transfer coefficient is of the form of Kutateladze’s (1961) power-type addition.
8.3.1 SUPERPOSITION MODELS

8.3.1.1 Chen Correlation
Chen (1966) proposed a general correlation for saturated boiling in a vertical tube.
His correlation is based on the superposition model, which divides the heat transfer
into two parts: a nucleate pool boiling contribution (hnb) based on Foster and Zuber’s
pool boiling equation (1955) and a bulk convective contribution (hbc) based on Dittus
and Boelter’s (1930) equation, as shown in Equations 8.1 through 8.3,
h = hnb + hbc (8.1)
kl 0.8 0.4
hbc = 0.023 Retp Prl (8.2)
D
where
Retp = two-phase Reynolds number
G (1 − x ) D
Retp = F ( X tt )1.25
µl
where
F(Xtt) = two-phase correction factor
F(Xtt) = 1.0 for Xtt ≥ 10

F(Xtt) = 2.35(0.213 + Xtt–1)0.736 for Xtt < 10
Xtt = Martinelli’s parameter
0.5 0.1
 Dv   µv 
{ }
0.9
Xtt = (1 − x ) /x  D   µ 
l l
 k 0.79Cp0.45ρ0.49  0.24 0.75

hnb = 0.00122  0l.5 0.29 l 0.24 l 0.24   Tw − Tsat ( Pl )   Psat (Tw ) − Pl  S (8.3)
 σ µ l h fg ρ fg 
where
S = two-phase correction factor
( ) ( )
−1
S Re tp = 1 + 2.56 × 10 −6 Re1tp.17
In this correlation, the nucleate boiling term is suppressed by a two-phase

correction factor (S) as the vapor quality increases. This factor accounts for the
thinner boundary layer at a higher vapor quality. The bulk convection term is
enhanced by a two-phase correction factor F(Xtt) as the vapor quality increases. This
factor accounts for the higher vapor velocities at the higher vapor quality. The Chen
correlation was developed to fit flow boiling data for water, methanol, cyclohexane
and pentane.
8.3.1.2 Bennett and Chen Correlation
Bennett and Chen (1980) modified the Chen correlation to account for the analysis
of nucleate boiling near the wall and for the effects of a liquid Prandtl number higher
than 1 on the bulk convection. Moreover, this correlation is based on experiments
with an aqueous mixture of ethylene glycol and water in a vertical channel. The
bulk convection term (hbc) was modified, as shown in Equation 8.4. The two-phase
correction factor was also modified, as shown in Equation 8.5,
hbc = hl F ( X tt ) Prl0.296 (8.4)
where
hl = liquid phase heat transfer coefficient
kl 0.8 0.4
hl = 0.023 Rel Prl
D
 − F ( X tt )hl X o 
1− exp  
 kl
S= (8.5)
F ( X tt )hl X o
kl
0.5
 σ 
where X o = 0.04 
 g(ρl − ρv ) 
As shown in Equation 8.5, this correlation includes the surface tension and
density difference between liquid and vapor phases in the nucleate boiling suppres-
sion factor. The heat transfer enhancement factor (F) includes thermal characteristics
of the fluid.
Ross et al. (1987) suggested the use of Bennett and Chen correlation with the
two-phase correction factor S set to zero. They proposed this idea based on their
experiment on the convective boiling heat transfer coefficient of R152a/R13B1. Since
the nucleate boiling is suppressed, the evaporation is the main heat transfer mech-
anism for the binary mixtures.
8.3.1.3 Gungor and Winterton Correlation
Gungor and Winterton (1986) developed the following correlation for flow boiling
in horizontal and vertical tubes. They used the basic form of the Chen correlation
in superposition form, as shown in Equation (8.6):
h = Ehl + Sh pool (8.6)
where
hl = heat transfer coefficient for the liquid phase flowing alone
E= forced convection enhancement parameter
S= forced convection suppression parameter
hpool = 55P γ 0.12 (− log10 P γ )−0.55 M −0.5q 0.67
E = 1 + 24000 Bo1.16 + 1.37 X tt−0.86
S = (1 + 1.15 × 10 −6 E 2 Re1l .17 )−1
In this correlation, two-phase correction factors (E and S) were obtained itera-

tively from over 4300 data points for water, various refrigerants and ethylene glycol,
covering seven fluids. Gungor and Winterton chose the Cooper (1984) correlation
for the pool boiling heat transfer coefficient.
8.3.1.4 Jung Correlation
Jung et al. (1989a) developed the following flow boiling correlation for horizontal
tubes for the binary mixtures R22/R114 and R12/R152a. They used the basic form
of the Chen correlation in superposition form similar to Gungor and Winterton’s as
shown in Equation 8.7,
h = Cme Fhl + S /Cun h pool (8.7)
where
Cme = 1 – 0.35|Xv – Xl|1.56
F = forced convection enhancement parameter
F = 2.37(0.29 + 1/Xtt)0.85
hl = heat transfer coefficient for the liquid phase flowing alone (Equation 8.5)
S = forced convection suppression parameter
S = 4048Xtt 1.22BO1.13 for Xtt < 1
S = 2 – 0.1Xtt –0.28BO–0.33 for 1 < Xtt < 5
Cun = |1 + (b2 + b3)(1 + b4)|(1 + b5)
hpool = hi /Cun
where
hi = ha hb /(hb Xl + ha Xv)
Xl = liquid phase composition

Xv = vapor phase composition
ha hb = pool boiling heat transfer coefficient of pure refrigerants a and b given
by Stephan and Abdelsalam (1981) correlation
b2 = (1 – Xl) ln|(1.01 – Xl)/(1.01– Xv)| + Xl ln(Xl /Xv) + |Xl – Xv|1.5
b3 = 0 for Xl ≥ 0.01
b3 = (Xl /Xv)0.1 – 1 for Xl < 0.01
b4 = 152(P/Pca)3.9
b5 = 0.92|Xl – Xv|0.001 + (P/Pca)0.66
Xl /Xv = 1 for Xl = Xv = 0
where
Pca = critical pressure of more volatile component
Jung et al. reported that this correlation matches their experimental data for
R22/R114 (23/77, 48/52, 77/23 wt.%) over 1700 data points and R12/R152a (21/79,
88/12 wt.%) within 9.6% deviation.
8.3.2 ENHANCEMENT MODELS

8.3.2.1 Shah Correlation
For saturated flow boiling in vertical and horizontal tubes, Shah (1976) proposed
the enhancement model, which enhances the single-phase heat transfer coefficient
of flowing liquid by a two-phase enhancement factor as shown in Equation 8.8. He
classified the flow-boiling regime into three regions by utilizing three dimensionless
parameters, shown in Equation 8.8. They are the pure nucleate boiling regime, the
bubble suppression regime and the convective boiling regime:
(
ψ s = h /hl = f Co, Bo, Frle ) (8.8)
where
Co = [(1 – x)/x]0.8 [ρv /ρl]0.5
Bo = (q11)/(Ghlv)
Frle = (G2)/(ρl2gD)
Initially, he presented this correlation graphically; later, he recommended the

following computational representation of his correlation as shown in Equation 8.9
(Shah, 1982):
Ns = Co for Frle ≥ 0.04 (8.9)
Ns = 0.38Frle–0.3 Co for Frle < 0.04

Fs = 14.7 for Bo ≥ 11 × 10–4
Fs = 15.4 for Bo < 11 × 10–4
ycb = 1.8Ns–0.8 for Ns > 1.0
ynb = 230Bo0.5 for Bo > 0.3 × 10–4
ynb = 1 + 46Bo0.5 for Bo ≤ 0.3 × 10–4 for Ns ≤ 1.0
ybs = Fs Bo0.5 exp(2.74 Ns–0.1) for 0.1 < Ns ≤ 1.0
ybs = Fs Bo0.5 exp(2.74 Ns–0.15) for Ns ≤ 0.1
ys = the larger of ynb and ycb for Ns > 1.0
ys = the larger of ybs and ycb for Ns ≤ 1.0
Wattelet et al. (1994a) examined Shah’s correlation with their experimental data
for R22/R124/R152a and reported that Shah’s correlation overestimates the exper-
imental data by more than 50% in the wavy-stratified flow regime, but matches well
with the experimental data in the annual flow regime.
8.3.2.2 Schrock and Grossman Correlation
Schrock and Grossman (1959) developed the following correlation based on a fit to

water in a vertical tube. This correlation is an enhancement model like Shah’s as
shown in Equation 8.10,
(
h /hl = C1 Bo + C2 X tt−0.66 ) (8.10)
where
Bo = boiling number
Cl = 7.39 × 10–3
C2 = 1.5 × 10–4
8.3.2.3 Mishra Correlation
Mishra et al. (1981) developed the following correlation based on their data fit to
R12/R22. This correlation is an enhancement model like Shah’s and very similar to
Schrock and Grossman’s, as shown in Equation 8.11,
h /hl = C1Bon X tt− m (8.11)
where
Cl = 5.64 for 23–27 wt.% of R12 and 21.75 for 41–48 wt.% of R12
m = 0.23 for 23–27 wt.% of R12 and 0.29 for 41–48 wt.% of R12
n = 0.15 for 23–27 wt.% of R12 and 0.23 for 41–48 wt.% of R12
8.3.2.4 Sami Correlation
Sami et al. (1992) developed their correlation Equation 8.12 for mixtures in an
enhanced tube — that is, an enhancement model in a form of the Dittus and Boelter
equation. However, Sami’s correlation uses a thermal conductivity term instead of
the Prandtl number.
h = 0.155(kl /D) A Re 0.62 kl0.3 (8.12)
where
kl = thermal conductivity of liquid
A = 1 – C(∑|XL – XV|)0.82
C = 0.79 for mixtures with HFCs
C = 0.68 for mixtures with HCFCs
Sami et al. (1992) developed this correlation with R22/R152a/R114 (53/19/28

wt.%) and R22/R152a/R124 (50/20/30 wt.%). Later, Sami et al. (1995) reported that
this correlation matches their experimental data for R23/R22/R134a (5/90/5 wt.%),
R23/R22/R152a (5/90/5 wt.%), R23/R125/R152a (8/62/30 wt.%) and
R23/R22/R134a (5/65/30 wt.%) within a 20% deviation.
8.3.2.5 Shin Correlation
Shin et al. (1996) developed the following correlation Equation 8.1 based on a fit to
R32/R134a and R290/R600a data of three compositions (75/25, 50/50, 25/75 wt.%).
This correlation is an enhancement model like Shah’s and used a correction factor
to account for the mass transfer effect due to the composition difference between
liquid and vapor phases, considered a driving force for mass transfer at the interface:
h /hl = (1 − CF ) F (8.13)
where
F = Chen’s two-phase correction factor
CF = A|Y – X|n
where
A = curved fitted coefficients (0.569 for R32/R134a; 0.533 for R290/R600a)
n = curved fitted coefficients (0.860 for R32/R134a; 0.828 for R290/R600a)
X = liquid phase composition

Y = vapor phase composition
This correlation matches with experimental data within a 9% deviation for

R32/R134a and 15% for R290/R600a.
8.3.3 ASYMPTOTIC MODELS

8.3.3.1 Liu and Winterton Correlation
Liu and Winterton (1991) proposed the following correlation for flow boiling inside
tube and annuli. They utilized an asymptotic model based on Kutateladze’s (1961)
power-type addition, as shown in Equation 8.14,
h = (Ehl )2 + (Sh pool )2 (8.14)
where
E = [1 + xPrl (ρl /ρv – 1)]0.35
S = (1 + 0.055E0.1 Rel0.16)–1
In this correlation, two-phase correction factors (E and S) were obtained from

4300 data points for water, various refrigerants and ethylene glycol fluids. The
Cooper (1984) correlation is used as a pool boiling heat transfer coefficient.
8.3.3.2 Wattelet Correlation
Wattelet et al. (1994b) proposed an asymptotic model based on their data for R12
and R134a. The Wattelet correlation accounted for the decrease in heat transfer due
to the wavy-stratified flow pattern in the low mass fluxes by adding a Froude
dependence to the convective term, as shown in Equation 8.15,
1/ 2.5
h =  hnb 2.5 + hbc 2.5  (8.15)
where
hnb = 55 M −0.5q 0.67 Pr0.12 [− log10 Pr ]−0.55
where
M = molecular weight
q = heat flux [W/m2]
Pr = reduced pressure
hbc = Fhl R
where
F = 1 + 1.925Xtt–0.83
hl = 0.23Rex0.8 Pr0.4 λl /D
R = 1.32Frl0.2 if Frl < 0.25
R = 1 if Frl ≥ 0.25
where
Frl = (G/ρl)2/(9.80665D)
8.3.3.3 Bivens and Yokozeki Correlation
Bivens and Yokozeki (1994) suggested a modified Jung correlation and Wattelet
correlation for R32/R125 and R32/R125/R134a to account for the mass transfer
resistance, as shown in Equation 8.16,
{
h = htp / 1+ htpTint /q } (8.16)
where
q = heat flux [W/m2]
Tint = temperature at the liquid-vapor interface
  q  
Tint = 0.175(Td − Tb ) 1 − exp  − −4 
  1.3 × 10 ρl h fg  
where
Td = dew point temperature [˚C]
Tb = bubble point temperature [˚C]
ρl = liquid density [kg/m3]
hfg = heat of vaporization [J/kg]
htp = heat transfer coefficient
1/ 2.5
htp =  hnb 2.5 + hbc 2.5 
where
hnb = 55 M −0.5q 0.67 Pr0.12 [− log10 Pr ]−0.55
hbc = Fhl R
where
F = (0.29 + 1/Xtt)0.85
R = 2.838Frl0.2 if Frl ≤ 0.25
R = 2.15 if Frl > 0.25
8.3.4 COMPARISON OF CORRELATIONS

Judge (1996) compared five flow boiling correlations in his cycle simulation study
to determine which works best with the simulation to predict the overall heat
transferred for residential air-conditioning and heat pumping applications with R22
and R407C. The flow boiling heat transfer correlations examined in his study were
Chen (1966), Gungor and Winterton (1986), Shah (1982), Jung (1989a) and Kandlikar
(1991). Jung and Kandlikar’s correlations were the only ones among these five
correlations developed for mixtures. These correlations are generally applicable to
any binary mixture of halogenated refrigerants.
The simulation results are presented by plotting the measured capacity vs. the
capacity predicted by the model. The evaporation results are shown in Figure 8.3.1.
When using Jung’s heat transfer correlation (providing the best results), the maxi-
mum difference between the simulation and experimental results ranges from –5.0
to +3.8%. Figures 8.3.2 and 8.3.3 show the flow boiling heat transfer coefficient vs.
position for the different heat transfer correlations for R22 and R407C, respectively.
Note that in Figure 8.3.3 all but one of the pure component heat transfer correlations
predict lower heat transfer coefficients than does Jung. This was not anticipated
because the pure component heat transfer correlations do not take into account the
degradation in heat transfer associated with mixtures. The other correlation devel-
oped for mixtures, Kandlikar’s, predicts heat transfer coefficients that are signifi-
cantly lower than that of Jung. This is particularly interesting since Kandlikar used
Jung’s data to develop his correlation.
8.4 PRESSURE DROP DURING EVAPORATION

In this section, some of the recent experimental data and correlation research on
horizontal boiling flow and pressure drop of mixtures are summarized. The pressure
drop in a pipe consists of three major contributions: frictional pressure drop (∆Pf ),
accelerational pressure drop (∆Pa) and gravitational pressure drop (∆Pg). For the
horizontal tube, the gravitational pressure drop is eliminated (∆Pg = 0). Moreover,
the accelerational pressure drop is generally much smaller than the frictional pressure
drop; therefore, most investigators only consider the frictional pressure drop. Two
major parameters of the frictional pressure drop are the liquid viscosity and mass
flux.
8.4.1 MARTINELLI AND NELSON CORRELATION

The Martinelli and Nelson (1948) correlation is one of the best accepted correlations
for the pressure drop during convective boiling in a horizontal tube, shown in
Equation 8.17. This correlation is based on a two-phase slip flow model:
2 f f 0G 2 L  1  G2  x 2  ρl  (1 − x )2 
∫
x
∆PMN =  φ2f 0 dx  +   + − 1 (8.17)
Dρl  x 0  ρl  α  ρv  (1 − α ) 
14 +5% 14 +5%
12 -5% 12 -5%
Predicted Capacity [kW]

10 10
8 8
6 6
4 4
2 JUNG 2 GUNGOR
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
Measured Capacity [kW] Measured Capacity [kW]
14 +5%
12
−5 %
10
4
SHAH
2
0
0 2 4 6 8 10 12 14
Measured Capacity [kW]
14 +5% +5%
14
12 −5 % 12 −5 %
10 10
8 8
6 6
4 4
CHEN KANDLIKAR
2 2
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
FIGURE 8.3.1 Flow boiling heat transfer correlation results (Judge, 1996).
where
∆PMN = Martinelli and Nelson total two-phase pressure drop
ff0 = frictional coefficient considering two-phase flow as liquid flow
G = mass flux
x = vapor quality

10
Heat Transfer Coefficient [kW/m-K] Jung Chen
9
Gungor Kandlikar
8 Shah
7
6
5
4
3
2
1
0
0 0.2 0.4 0.6 0.8 1
Relative Heat Exchanger Length
FIGURE 8.3.2 Evaporation heat transfer coefficient vs. length (R22) (Judge, 1996).
10
Heat Transfer Coefficient [kW/m-K]
Jung Chen
9
Gungor Kandlikar
8 Shah
7
6
5
4
3
2
1
0 0.2 0.6 1
0 0.4 0.8
FIGURE 8.3.3 Evaporation heat transfer coefficient vs. length (R407C) (Judge, 1996).
L = length
D = tube diameter
ρv = vapor density
φ2f 0 = two-phase frictional multiplier
α = void fraction
The Blasius friction factor relation for the turbulent flow in a smooth pipe as
shown in Equation 8.18 can be used to obtain the frictional coefficient (ff 0):

f fo = 0.079 Re −0.25 (8.18)
The frictional pressure drop when the total flow is liquid is given in Equation 8.19,
2 f f 0G 2 L 2
∆Pf ,MN = φf0 (8.19)
Dρl
To obtain the total pressure drop during the evaporation, the Martinelli and
Nelson correlation requires the evaluation of the local two-phase frictional multiplier
(φ2f0) and void fraction (α). Wallis (1969) gave the following relations (Equations
8.20 and 8.21) for these two parameters:
φ2f 0 = φl2 (1 − x )1.75 (8.20)
2
 1 
where φl =  1 + 0.5 
 x 
α = (1 + x 0.8 )−0.378 (8.21)
Ross et al. (1987) compared their experimental data for R13B1/R152a (18/82,
38/62 and 80/20 wt.%) with Chisholm’s (1967) correlation, a modified version of
the Martinelli and Nelson method. They reported that the Chisholm correlation
matches with their data within a 30% variation and there is no need to modify the
Chisholm correlation.
8.4.2 SINGAL CORRELATION

Singal et al. (1983) studied the pressure drop of R12 and R13/R12 (5/95, 10/90 and
15/85 wt.%) during evaporation and reported that the Martinelli and Nelson corre-
lation overpredicts the pressure drop of R12 and underpredicts the pressure drop of
R13/R12 mixtures. Singal et al. then suggested two sets of total pressure drop (∆Ptp)
correlations (Equations 8.22) and two sets of frictional pressure drop (∆Pf) correla-
tions (Equations 8.23) by modifying the Martinelli and Nelson correlation:
∆Ptp = 0.87(1 + C)2.66 ∆PMN

(8.22)
∆Ptp = 0.89(1 − C)−2.12 ∆PMN
∆Pf = 0.86(1 + C )2.86 ∆Pf ,MN

(8.23)
∆Pf = 0.88(1 − C )−2.28 ∆Pf ,MN

Singal et al. reported that these correlations match their data within a 30%
deviation. However, these correlations cannot be used for R13 mass fractions larger
than 25%.
8.4.3 SAMI CORRELATION

Sami et al. (1992) suggested the following correlation (Equation 8.24) using the Bo
Pierre (1954) form based on their measurement of R22/R152a/R114 and
R22/R152a/R124 in an enhanced tube. The Pierre correlation is a semi-empirical
correlation based on a two-phase homogeneous model. Sami’s correlation matches
the experimental data within a 15% deviation. Later, Sami et al. (1995) examined
their correlation against their data for additional mixtures R23/R22/R152a (5/90/5,
5/65/30 wt.%), R23/R22/R290 (5/90/5 wt.%), R23/R22/R134a (5/65/30 wt.%) and
R23/R125/R152a (8/62/30 wt.%) and reported the mean deviation is 30% for most
of the data.
 ( x − x )D  G2 L
∆Ptp =  favg + 2 1  (8.24)
 xavg L  Dρavg
where
favg = 0.43 Kf 0.3 Re–0.28
Kf = Bo Pierre number
Kf = ∆x hfg /L
ρavg = ρv ρl [xavg ρl + (1 – xav) ρv]
xavg = (xi + xo)/2
8.4.4 JUNG AND RADERMACHER CORRELATION

Jung and Radermacher (1989) studied the pressure drop of R12, R22, R114, R152a
and R12/R152a. They reported that the Pierre correlation is not applicable to half
of their data and the Martinelli and Nelson correlation overpredicted their data by
20% but is applicable. The authors suggested a modified version of the Martinelli
and Nelson correlation, as shown in Equation 8.25. Their correlation matches their
data for both pure fluids and mixtures within an 8% deviation.
2 f f 0G 2 L  1 
∫
x2
∆Ptp =  φtp2 dx  (8.25)
Dρl  ∆x x1 
where
f fo = 0.079 Re −0.25
φtp2 = 30.78 x1.323 (1 − x )0.477 Pr−0.7232

8.4.5 SOUZA AND PIMENTA CORRELATION

Souza and Pimenta (1995) studied the pressure drop of R12, R22, R134a, R152a,
R22/R152a/R124 and R32/R125. They reported that flow regimes were predomi-
nantly annular flow and stratified-wavy flow for high mass fluxes and low mass
fluxes, respectively. The authors suggested a modified version of Chrisholm’s (1973)
separate flow model for a frictional pressure drop, as shown in Equation 8.26. Their
correlation matches their data for both pure fluids and mixtures within an 8%
deviation.
2 f f 0G 2 L  1 
∫
x2
∆Ptp =  φtp2 dx  (8.26)
Dρl  ∆x x1 
where
f fo = 0.079 Re −0.25
φtp2 = 1 + (Γ 2 − 1) x1.75 (1 + 0.9524 ΓX tt 0.4126 )
where
0.5 0.125
ρ   µv 
Γ= l  µ 
 ρv  l
8.4.6 OTHER STUDIES

There are two interesting issues regarding the pressure drop of mixtures as compared
to the pure fluids. The first is whether the pressure drop of mixtures is higher or
lower than that of pure fluids. Torikoshi and Ebisu (1993) studied the pressure drop
of R32/R134a (30/70 wt.%) and reported it follows an ideal pressure drop as
predicted by the linear interpolation of the values of the pure fluids, as shown in
Figure 8.4.1. This behavior is somewhat different from the boiling heat transfer
behavior of mixtures as compared to that of pure fluids.
The second issue is whether the pressure drop of an alternative refrigerant
mixture is higher or lower than that of the pure fluids it is supposed to replace.
Wijaya and Spatz (1995) studied the pressure drop of R32/R125 (50/50 wt.%) during
evaporation and found that R32/R125 results in approximately 24 to 38% lower
pressure drop than that of R22.
8.5 CONDENSATION HEAT TRANSFER COEFFICIENTS

In this chapter, research on condensation heat transfer is summarized. The summary
is limited to condensation in horizontal tubes since most of the condensers used for
refrigeration and air-conditioning applications are oriented horizontally. Table 8.3
summarizes the latest research on the condensation heat transfer coefficients of

5
G=91 [kg/m2 -s]
G=182 [kg/m2 -s]
Pressure Drop [kPa/m] 4 R22, G=91
R22, G=182
0
0.0 0.2 0.4 0.6 0.8 1.0
R-32 Composition
Ts = 5°C
FIGURE 8.4.1 Pressure drop of R32/R134a during evaporation (Torikoshi and Ebisu, 1993).
TABLE 8.3
In-tube Condensation Research
Mass Flux
Authors Refrigerant [kg/m2-s] Tube/ID [mm]
Stoecker and Kornota (1985) R12/R114 173 Plain/13

Tandon (1986) R22/R12 170–530 Plain/10
Koyama et al. (1990) R22/R114 133–358 Microfin/8.3
Conklin and Vineyard (1991) R143a/R124 200–500 Finned/13.7,
Fluted/16.8
Sami et al. (1992) R22/R152a/R114, 142–255 Fluted/21.2
R22/R152a/R124 142–255 Fluted/21.2
Sami et al. (1993) R22/R114, R22/R152a 333–776 Microfin/8.3
Sami et al. (1995) R23/R22/R152a
Torikoshi and Ebisu (1993) R32/R134a 100–400 Plain/8.7
Doerr et al. (1994) R32/R125, R32/R134a, 125–375 Plain/OD 9.5
R32/R125/R134a,
R125/R143a/R134a
Ro et al. (1994) R32/R134a 192 Plain/7.6
Dobson and Chato (1998) R32/R125 25–800 Plain/3.14, 7.04
Wijaya and Spatz (1995) R32/R125 160–561 Plain/7.8
Wang et al. (1996) R407C 100–300 Plain/7.9
Eckels and Tesene (1999) R410a, R407C 125–600 Plain/8.0
Microfin/8.9, 14.6, 7.3
Note: ID: Inside diameter, OD: Outside diameter.
Source: Wang and Chato, 1995.

mixtures based on Wang and Chato’s (1995) summary and an additional survey of
the latest literature. Wang and Chato pointed out that the main focus of the recent
research on condensation heat transfer with mixtures is on:
• Thermal resistance of the vapor diffusion layer affecting the condensation.

• Influence of the flow direction of vapor during the condensation (horizon-
tal tube or vertical tube).
• Turbulence in the vapor generated by fins.
• Enhancement of the condensation performance of mixtures.
During the mixture condensation process, the higher boiling component transfers
into condensate at the vapor-liquid interface more so than the lower boiling com-
ponent because in the condensate, the mass fraction of the high boiling point
component is higher than in the vapor phase. More of the lower boiling point com-
ponent diffuses into the vapor mixture away from the interface. This mass fraction
gradient causes the deterioration of condensation heat transfer at the interface.
Therefore, the greater volatility difference between the mixture components results
in lowering the condensation heat transfer. This resistance to condensation heat
transfer is similar to that of evaporation heat transfer. The resistance is seen as being
caused by the originating phase.
Stoecker and Kornota (1985) investigated the condensation heat transfer coeffi-
cients of R12/R114. They divided the condenser into two parts, a high temperature
condenser and a low temperature condenser. Their results can be summarized as
follows:
• In the beginning of the high temperature condenser where the desuper-

heating occurs, no change of mixture mass fraction occurs and there is
no effect on the condensing heat transfer coefficients.
• In the last part of the high temperature condenser where the phase changes,
that is the midrange of the condenser, the condensing heat transfer coef-
ficients are highest and have the most dominant changes. As the R114
mass fraction increases, the heat transfer coefficients decrease.
• Stocker and Kornota explained this heat transfer coefficient degradation
by the slip between the liquid and vapor. No slip condition is assumed
when modeling two-phase flow at low vapor velocities. However, when
two-phase flow at high vapor velocities are considered, the vapor velocity
at the liquid-vapor interface can exceed that of the liquid. This slip con-
dition creates a local nonequilibrium state between the two phases with
respect to temperature and mass fraction during the condensation of the
mixtures.
Tandon et al. (1986) investigated the condensation heat transfer coefficients of

R22/R12. They reported that the condensing heat transfer coefficients of mixtures
are lower than those of R22 and higher than those of R12.

Koyama et al. (1990) investigated the condensing heat transfer coefficients of

R22/R114 mixtures in a horizontal tube, then reported their results as follows:
• The local condensing heat transfer coefficients of the mixtures are smaller
than those of pure refrigerants.
• The condensing heat transfer coefficients of a zeotropic mixture are
enhanced in a microfin tube by about 30% as compared to a plain tube.
This enhancement is only half as much compared to that of the pure
refrigerant enhancement.
• The maximum degradation of the condensing heat transfer coefficient of
R22/R114 is about 20% at 34 to 43 wt.% of R22 mass fraction.
• The circumferential wall temperature distribution is somewhat different
from that of the pure refrigerants. For R22, the circumferential wall
temperature variation is small at the entrance but gradually increases in
the flow direction, indicating the flow pattern changes from the annular
flow to semiannular flow. The circumferential wall temperature of R22
decreases from the right, top, bottom and left since the thin liquid film at
the top moves to the right and the thick liquid film at the bottom moves
to the left due to the internal groove. For R22/R114 mixtures, the circum-
ferential wall temperature is uniform, which might be due to the opposite
changes of liquid-vapor interfacial temperature distribution.
Conklin and Vineyard (1991) studied the condensing heat transfer coefficient of
R143a/R124 (30/70, 51/49, 73/27 and 77/23 wt.%) in a finned tube and fluted tube.
They reported that the condensing heat transfer coefficients of theses binary mixtures
are higher in a finned tube than in a fluted tube. The condensing heat transfer
coefficients of R143a/R124 (30/70 wt.%) are about 15% higher than that of R22.
The pressure drop in the finned tube is only half of that in the fluted tube.
Sami et al. (1992) studied the condensing heat transfer coefficient of
R22/R152a/R114 (53/19/28 wt.%) and R22/R152a/R124 (50/20/30 wt.%) in a fluted
tube and reported the condensing heat transfer coefficient of these two ternary
mixtures is lower than R22 and higher than R12. No significant difference was found
between the condensing heat transfer coefficient of R22/R152a/R114 and
R22/R152a/R124. By using the same facility, Sami and Schnotale (1993) studied
the condensing heat transfer coefficient of R22/R114 and R22/R152a in a fluted
tube. As the R114 mass fraction increases, the condensing heat transfer coefficient
of R22/R114 increases almost linearly. However, the condensing heat transfer coef-
ficient of R22/R152a decreases as the R152a mass fraction increases. They also
found that the heat transfer coefficients of R22/R114 mixtures are lower than those
of R22 but the heat transfer coefficients of R22/R152a mixtures are higher than
those of R22.
Torikoshi and Ebisu (1993) studied the condensing heat transfer coefficient of
R32/R134a (30/70 wt.%). They reported the degradation of the condensing heat
transfer coefficient compared to the ideal condensing heat transfer coefficient as 36
and 29% for a mass flux of 91 kg/m2-s and 182 kg/m2-s, respectively, when the
saturation temperature was 50˚C.

TABLE 8.4
Ratio of In-tube Condensing Heat Transfer Coefficient to R22
R32/R125 R32/R134a R32/R134a
Condensing (60/40 (10/90 (25/75 R32/R125/R134a R125/R143a/R134a
Temperature wt.%) wt.%) wt.%) (30/10/60 wt.%) (44/53/4 wt.%)
30˚C 1.02 0.81 0.82 0.79 0.77

40˚C n/a 0.90 0.93 0.92 0.76
Mass flux: 200 kg/m2-s.
Source: Doerr et al., 1994.
Doerr et al. (1994) investigated the condensing heat transfer coefficients of

R32/R125 (60/40 wt.%), R32/R134a (10/90 and 25/75 wt.%), R32/R125/R134a
(30/10/60 wt.%) and R125/R143a/R134a (44/53/4 wt.%) in a horizontal tube and
compared those with R22. As summarized in Table 8.4, only R32/R125 (60/40 wt.%)
has a slightly higher heat transfer coefficient than R22. The other mixtures have a
lower heat transfer coefficient than R22 by 4 to 7%.
Ro et al. (1994) investigated condensing heat transfer coefficient of R32/R134a
(30/70 wt.%) and compared it with that of R22. Their results are:
• The heat transfer coefficient of R32/R134a (30/70 wt.%) is 10 to 20%

lower than that of R22.
• The condensing heat transfer coefficient increases at lower vapor qualities
as the vapor quality increases. However, the condensing heat transfer
coefficient decreases at the higher vapor quality as the vapor quality
increases. These characteristics are also represented by the existing cor-
relations such as Chen (1966), Soliman et al. (1968) and Traviss (1973)
that are based on the annular flow assumption. In the annular flow regime,
the heat transfer coefficient decreases because the growing liquid layer
around the tube increases thermal resistance.
• The condensing heat transfer coefficients of the mixture match better with
these correlations at the higher vapor quality where the flow regime
experiences annular flow. Most of the data fell in the annular flow regime.
The mean deviation of theses correlations with the data is about 30%.
Wijaya and Spatz (1995) reported that the condensing heat transfer coefficient
of R410A is slightly higher (about 3 to 6%) than that of R22 at low refrigerant
quality since the liquid thermal conductivity of R410A is as much as 8% lower than
that of R22 and its viscosity is 30 to 36% lower than that of R22.
Wang et al. (1996) compared the condensing heat transfer coefficient of R22
and R407C. They reported that the heat transfer coefficient of R407C is only 30 to
50% that of R22. The heat transfer coefficient of R407C is not very dependent upon
the changes of condensing pressure though the heat transfer coefficient of R22
increases as the condensing pressure increases.

Eckels and Tesene (1999) compared the condensing heat transfer coefficients of
R22, R134a, R410A and R407C in a smooth tube and microfin tubes. Their results
are:
• The condensing heat transfer coefficients for the microfin tube are signif-
icantly higher than those for the smooth tube for all refrigerants tested.
• R134a has the highest heat transfer coefficients in both types of tubes
while R407C has the lowest HTCs in both types of tubes.
• The heat transfer coefficient enhancement of the microfin tube over the
smooth tube varies from 2.2 to 2.5 at the lowest mass flux and from 1.2
to 1.6 at the highest mass flux. However, only R407C has a lower enhance-
ment at the lowest mass flux. This enhancement can be explained by the
turbulence enhancement by the internal fins that delay the flow pattern
transition from the annular flow to wavy flow.
8.6 CORRELATIONS FOR FLOW CONDENSATION

HEAT TRANSFER
For modeling purposes, accurate heat transfer correlations for mixtures are needed
to properly design heat exchangers. This section presents literature survey results
from a screening of condensation heat transfer correlations.
In this section, four well-known condensing heat transfer correlations for pure
fluids are introduced — Akers, Traviss, Shah and Dobson — and four recent corre-
lations for mixtures — Tandon, Koyama, Sami and Sweeney — are explained. The
applicability of these general correlations for mixtures must be proven.
8.6.1 AKERS CORRELATION

Akers et al. (1959) developed the following correlation (Equation 8.27) for the
turbulent annual film flow that is only valid for pure fluids.
kl 0.8 1/ 3
h = 0.0265 Reeq Prl ,Reeq > 5 × 10 4
D
(8.27)
k
h = 5.03 l Re eq
0.8
Prl1/ 3 ,Re eq < 5 × 10 4
D
where
Reeq = Reynolds number at equivalent mass flux given by Equation 8.28
0.5
µ  ρ 
Reeq = Rels + Re vs  v   l  (8.28)
 µ l   ρv 

where
Rels = GD (1 – x)/µl
Revs = GDx/µv
8.6.2 TRAVISS CORRELATION

Traviss et al. (1973) proposed the following semi-empirical correlation (Equation 8.29)
based on their experimental data with R12 and R22 in a horizontal smooth tube.
kl Re 0.9 Prl
h= F ( X tt ) l (8.29)
D F2
where
F ( X tt ) = 0.15 X tt −1 + 2.85X tt −0.476
0.1 0.9 0.5 (8.30)

µ   1− x   ρv 
X tt =  l   x   ρ 
 µv  l
F2 = 0.707 Prl Re l0.5 for Re l < 50
F2 = 5 Prl + 5 ln 1 + Prl (0.09636 Rel 0.585 − 1)  for 50< Re l < 1125 (8.31)
F2 = 5 Prl + 5 ln(1 + 5 Prl ) + 2.5 ln(0.00313 Rel0.812 ) for Rel > 1125
8.6.3 SHAH CORRELATION

For predicting the heat transfer coefficients during film condensation inside pipes,
Shah (1979) proposed an enhancement model that enhances the single-phase heat
transfer coefficient of flowing liquid by a two-phase enhancement factor, as shown
in Equation 8.32. This correlation was compared with many pure fluids such as
water, R11, R12, R22, R113, methanol, ethanol, benzene, toluene and trichloroeth-
ylene. The mean deviation was 15.4%.
 3.8 x 0.76 (1 − x )0.04 

h = hl  (1 − x )0.8 +  (8.32)
 Pr 0.38 
where
hl = single-phase liquid heat transfer coefficient by Dittus and Boelter equation

8.6.4 DOBSON CORRELATION

Dobson et al. (1994) developed their correlations for the annular- and wavy-flow
regime (Equations 8.33 and 8.34, respectively) for R12 and R134a in a smooth tube
that is of similar form as Dittus and Boelter’s and Chato’s correlations, respectively.
They reported that these correlations match their data within a 7% deviation:
h=
kl
D
( )
0.023 Rel0.8 Prl0.4 1 + 2.22 X tt−0.89 for annual-flow regime (8.33)
kl  0.23 Re 0v .12  Ga Prl  

h=  0.58   + (1 − θl /π) Nu f  for wavy-flow regime (8.34)
D  1 + 1.11X tt  Jal  
where
Nu f = 0.0195 Rel0.8 Prl0.4 φl ( X tt )
where
C1
φl ( X tt ) = 1.376 +
X tt c2
where
c1 = 4.12 + 0.48Frl – 1.564Frl2
c2 = 4.12 + 0.48Frl – 1.564Frl2 for 0 < Frl ≤ 0.7
c1 = 7.242
c2 = 1.655 for Frl > 0.7
where
Frl = liquid Froude number
θl = angle subtended from the top of tube to the liquid level
θl arccos(2α − 1)
1− ≅ by Jaster and Kosky (1976)
π π
8.6.5 TANDON CORRELATION

Tandon et al. (1986) proposed the following correlation (Equation 8.35) based on
their experimental data with R22/R12 mixtures in a horizontal tube. The mean
deviation was 15%:
kl −0.365
h = 2.82 Ph Re v 0.146 Prl1/ 3 (8.35)
D

where
h fg
Ph =
(
cPl Tsat − Tw )
8.6.6 KOYAMA CORRELATION
Koyama et al. (1990) proposed the following correlation (Equation 8.36) based on
their experimental data with R22/R114 mixtures in a horizontal microfin tube. Their
correlation is a modified version of Fujii and Nagata’s (1973).
0.4 0.8
kl  D   Re Pr 
h = 0.53 Ph −0.6  l l  (1 − 0.73X + 0.37 X 2 + 0.36 X 3 ) (8.36)
D  L   R 

Sami et al. (1992) developed their correlation (Equation 8.37) for mixtures of
R22/R152a/R114 (53/19/28 wt.%) and R22/R152a/R124 (50/20/30 wt.%) in an
enhanced tube that is of similar form as Koyama’s correlation. They reported that
this correlation matches with their data within a 10% deviation:
0.4 0.6
k  D −0.6  Rel Prl 
h = 6.4 l   Ph  R  (8.37)
D L
where
0.5
 ρµ 
R= l l 
 ρvµ v 
Later, Sami et al. (1995) reported that this correlation with a coefficient 0.212
instead of 6.4 matches with their experimental data for R23/R22/R134a (5/90/5 wt.%),
R23/R22/R152a (5/90/5 wt.%), R23/R125/R152a (8/62/30 wt.%) and R23/R22/R134a
(5/65/30 wt.%) within a 20% deviation.
8.6.8 SWEENEY CORRELATION

Sweeney (1996) and Sweeney and Chato (1996) correlated Kenney et al. (1994) data
for R407C in a smooth tube using Dobson’s correlations and suggested correlations,
Equations 8.38 and 8.39:
0.3
 G 
h = 0.7  h Eq. (8.36) for annual-flo
ow regime (8.38)
 300 
0.3
 G 
h= h Eq. (8.37) for wavy-flow reg
gime (8.39)
 300 

8.6.9 COMPARISON OF CORRELATIONS

Judge (1996) compared five flow condensation correlations in his cycle simulation
study to determine which one works best with the simulation to predict the overall
heat transferred. The flow condensation heat transfer correlations examined in his
study were: Tandon et al. (1986), Chen (1987), Traviss et al. (1973), Shah (1979)
and Dobson et al. (1994). Dobson’s correlation was developed for R32/R125 (50/50
wt.%) and Tandon’s correlation was developed from R22/R12 data for several
different mass fractions. The remaining correlations were developed for pure fluids.
The condensation results are presented in a similar format as the evaporation
results and can be seen in Figure 8.6.1. Dobson’s condensation correlation worked
best with Judge’s heat exchanger model; the maximum difference between the
simulation and experimental results ranges from –3 to +7%. Typical condensation
heat transfer coefficients vs. position in the heat exchanger are presented in Figures
8.6.2 and 8.6.3. The increased error in condensation relative to evaporation occurs
for two reasons. One is that none of the condensation heat transfer correlations were
developed to be generally applicable for any mixture. The other reason is that most
of the correlations considered were developed for the annular flow regime.
The heat exchanger simulation was used to generate points on Baker’s flow map
(Baker, 1954). Figure 8.6.4 is a flow map of R22 in evaporation and condensation,
respectively. For evaporation, a large fraction of the heat is absorbed in the annular
regime. Furthermore, the other region representing wavy flow is somewhat similar
to annular flow in that the entire circumference of the tube can be covered with
liquid. Hence, annular flow correlations are often used to approximate wavy flow.
In any event, Jung’s flow boiling correlation is not restricted to the annular flow
regime. At low mass fluxes, Jung’s correlation reduces to pool boiling, an attractive
aspect since the pool boiling represents the lower limit for all other boiling regimes.
For condensation, the flow map shows that a significant portion of the heat is rejected
in the slug and plug flow regimes. This is unfortunate since there exists very little
heat transfer data in these regimes. However, Dobson’s condensation correlation for
the annular flow regime reduces to a single-phase flow correlation as the quality is
reduced. Hence, Dobson’s correlation is accurate in the limits of single-phase flow
and annular flow and it is used to approximate the heat transfer coefficient for the
flow regimes between them. Furthermore, the sample size is not sufficiently large
to state that the heat exchanger model will predict the capacity for any heat exchanger
configuration within the errors reported here.
8.7 PRESSURE DROP DURING CONDENSATION

In this section, recent experimental research and correlations for horizontal condens-
ing flow pressure drop of mixtures are summarized. As mentioned in Section 8.4,
the pressure drop in a pipe consists of three major contributions: frictional pressure
drop (∆Pf), accelerational pressure drop (∆Pa) and gravitational pressure drop (∆Pg).
For the horizontal tube, the gravitational pressure drop is eliminated (∆Pg = 0).

+10% +10%
14 14
+5% +5%
−5% −5 %
12 12
−10% −10%

10 10
8 8
6 6
4 4
DOBSON TRAV ISS
2 2
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
14 +10%
+5%
−5%
12
−10%
10
2 SHAH
0 0 2 4 6 8 10 12 14
Measured Capacity [kW]
14 +10% 14 +10%
+5% +5%
12 −5% −5%
12
−10% −10%
10 10
8 8
6 6
4 4
2 CHEN TANDON
2
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
FIGURE 8.6.1 Condensation heat transfer correlation results (Judge, 1996).
Moreover, the accelerational pressure drop is generally much smaller than the fric-
tional pressure drop; therefore, most investigators only considered the frictional
pressure drop. Two major parameters of the frictional pressure drop are the liquid
viscosity and mass flux.

6
Heat Transfer Coefficient [kW/m-K] Tandon
5 Traviss
Shah
4 Chen
Dobson
3
0
0 0.2 0.4 0.6 0.8 1
FIGURE 8.6.2 Condensation heat transfer coefficient vs. length (R22) (Judge, 1996).
8
Heat Transfer Coefficient [kW/m-K]
Tandon
7
Traviss
6 Shah
Chen
5
Dobson
4
3
2
1
0
0 0.2 0.4 0.6 0.8 1
FIGURE 8.6.3 Condensation heat transfer coefficient vs. length (R407C) (Judge, 1996).
8.7.1 KOYAMA CORRELATION

Koyama et al. (1990) suggested the following correlation based on their experiment
with R22/R114 mixtures in a horizontal microfin tube. They reported their results
for frictional pressure drop are well-correlated by the Lockhart and Martinelli param-
eters within a 30% deviation, as shown in Equations 8.40 through 8.44:
∆P = ∆Pf + ∆Pm (8.40)

Evaporation (Outdoor Hx)

Evaporation (Indoor Hx)
Dispersed
Annular
100
Wavy
Gx (kg/m s)
2
Condensation
10 (Indoor Hx)
Bubbly
Slug
λ
Condensation
(Outdoor Hx)
Stratified
1.0
R-22 Plug
0.1
1.0 10 100 103 104
G(1−x)R
FIGURE 8.6.4 Baker’s flow map: Conditions for evaporation and condensation processes
are superimposed (Judge, 1996).
where
∆P = total two-phase pressure drop
∆Pf = frictional pressure drop
∆Pm = pressure drop due to the momentum change
G 2   x 2  ρl  (1 − x )2   x 2  ρl  (1 − x )2  
∆Pm =  +  − +  (8.41)
ρl   α  ρv  (1 − α)   α  ρv  (1 − α)  
2 1
where
G = mass flux
ρv = vapor density
x = vapor quality
α = void friction
−1
   x ρl /ρv + 0.4(1 − x )   
( )
0.5
  ρv   1 − x  
α = 1 +      0.4 + 0.6    (8.42)
  ρl   x
 

x + 0 .4 (1 − x )   
 
( )
∆Pf /∆z = ∆P /∆z v Φ 2v (8.43)
where
Φv = Lockhart and Martinelli parameter
 ∆P  2 fvG 2 x 2
 ∆z  = Dρ (8.44)
v v
where
∆Pv = vapor flow pressure drop
fv = frictional coefficient considering two-phase flow as vapor flow
D = tube diameter
The Colburn friction factor relation for the turbulent flow in a smooth pipe (as
shown in Equation 8.45) can be used to obtain the frictional coefficient (fv),
fv = 0.046 Re −0.2 (8.45)

Sami et al. (1992) suggested using the Lockhart and Martinelli parameters to calculate
the frictional pressure gradient based on their measurement of R22/R152a/R114 and
R22/R152a/R124 in an enhanced tube. The suggested correlation is shown in Equa-
tions 8.40 and 8.41. They correlated the friction factor using the form of Blasius as
shown in Equation 8.46:
f = 0.6 Re −0.21 (8.46)
The Sami correlation matches their experimental data within 30%. Later, Sami
et al. (1995) examined their earlier correlation against their data for other mixtures
of R23/R22/R152a (5/90/5 and 5/65/30 wt.%), R23/R22/R290 (5/90/5 wt.%),
R23/R22/R134a (5/65/30 wt.%) and R23/R125/R152a (8/62/30 wt.%) and reported
that the mean deviation is 15% for most of the data.
8.7.3 OTHER STUDIES

There are two interesting issues regarding pressure drop of mixtures as compared
to the pure fluids as mentioned in Section 8.4.6. The first is whether the pressure
drop of mixtures is higher or lower than that of pure fluid constituents. Torikoshi
and Ebisu (1993) studied the pressure drop of R32/R134a (30/70 wt.%) and reported
it follows an ideal pressure drop as predicted by the linear interpolation of the values
of the pure fluids. However, the pressure drop of R32/R134a (30/70 wt.%) is about
20% larger than that of R22. This behavior is somewhat different from the condens-
ing heat transfer behavior of mixtures as compared to that of pure fluids.
The second issue is whether the pressure drop of an alternative refrigerant

mixture is higher or lower than those of the pure fluids it is intended to replace.
Wijaya and Spatz (1995) studied the pressure drop of R32/R125 (50/50 wt.%) during
condensation and found that R32/R125 results in an approximately 25 to 45% lower
pressure drop than that of R22.
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9 Operational Issues
This chapter discusses operational and handling issues that are unique to refrigerant
mixtures. It is based on laboratory experience with refrigerant mixtures and guide-
lines by the U.S. Environmental Protection Agency (EPA) and the Air-Conditioning
and Refrigeration Institute (ARI) for the handling of refrigerants.
9.1 REGULATION
9.1.1 CLEAN AIR ACT AMENDMENTS OF 1990
In 1990, the Clean Air Act was amended to control the production and use of
refrigerants in the United States. The goal of these amendments was to reduce the
total use and emissions of chlorofluorocarbons (CFCs) and hydrochlorofluorocar-
bons (HCFCs) and to maximize recycling. Two pertinent sections to the Clean Air
Act, Sections 608 and 609, restrict the emissions of class I (CFCs) and II (HCFCs)
substances from service, repair and disposal operations on stationary equipment and
mobile applications, respectively. It is unlawful in the United States for any person
to knowingly vent, release or dispose of any class I and II substances used as a
refrigerant in appliances and industrial process refrigeration while maintaining,
servicing, repairing or disposing, effective July 1, 1992. The EPA has the authority
to write necessary regulations to implement the Clean Air Act.
9.1.2 EPA REGULATIONS

In 1993, the EPA set its regulations to enforce the Clean Air Act, which covers the
following five sections:
• Require technicians servicing and disposing of air-conditioning and refrig-

eration equipment to observe service practices that reduce refrigerants
emissions.
• Establish air-conditioning and refrigeration technician certification pro-
grams and restriction of the sale of refrigerants to certified technicians.
• Establish equipment and reclaimer certification programs.
• Require repair of substantial leaks.
• Implement safe disposal procedures.
Violations of the Clean Air Act are punishable by fines up to $25,000 per
violation per day and the possible loss of technician certification. However, the EPA
allows some minimal emissions in the course of handling of refrigerants and oper-
ation of equipment in the following cases:
279
• De minimis release if they occur, though all requirements for the proper
handling of refrigerants of allowed and approved recovery and recycling
machines are used.
• Refrigerant release from the equipment while in the normal operation,
such as purging and leaks.
• Nitrogen mixed with a small mass fraction of R22 for leak testing.
• Refrigerant release from hose purging or connections while charging or
servicing.
9.2 REFRIGERANT RECOVERY

First, it is necessary to define three terms for the handling of refrigerants that have
already been used. These are well defined by an ARI (1994) guideline:
1. Recovery: the transferring of refrigerants from a system or container to a

recovery container.
2. Recycling: the cleaning of refrigerants by oil separation, noncondensable
removal and reduction of moisture, acidity and particulate matter for reuse.
3. Reclaiming: a complicated distillation process that returns recovered
refrigerants to the purity of factory-new refrigerants.
Figure 9.2.1 shows a typical refrigerant recovery machine. Refrigerant recovery

needs to be done very carefully to minimize refrigerant emissions, as can be seen
in the following procedures:
• Prepare a recovery container that is approved by the Department of Trans-

portation (DOT) for recovery purposes. Figure 9.2.2 shows a typical 9 kg
recovery container.
• Evacuate the recovery container using a vacuum pump.
• Decide on a recovery method, either vapor recovery or liquid recovery,
according to feasibility. Vapor recovery is slow (0.5 to 0.9 kg/min) but
can remove most of the refrigerant from a system. While the liquid
recovery is fast, it cannot remove the refrigerant vapor remaining in the
system. For high pressure systems, vapor recovery is recommended.
• Before connecting any hoses to the system, make sure the system is off-
duty throughout the recovery process. If any (solenoid) valves are used
in the system, open the valves to enhance the recovery if possible.
• Connect the system service port, recovery container and recovery machine
with refrigerant hoses.
• Open valves between the system, recovery machine and recovery con-
tainer. Start the recovery machine.
• When the recovery container is filled to 80% of maximum (usually deter-
mined by weight), it should be disconnected and a new container should
be used.
Operational Issues 281
FIGURE 9.2.1 Refrigerant recovery machine. (Photo courtesy of INFICON.)
FIGURE 9.2.2 Recovery container. (Photo courtesy of Worthington Cylinder Corporation.)
9.3 CYCLE FLUSHING

When the system is retrofitted with another type of refrigerant and oil, the system
should be flushed. It is necessary to check the types of refrigerants and oils used
before and after the retrofit procedure. CFCs and HCFCs have mostly used mineral
oils; however, hydrofluorocarbons (HFCs) as alternatives for CFCs and HCFCs

require POE (Polyolester) oils. Many different types of POEs are available but some
compressor and system manufactures recommend only specific oils based upon their
own compressor life testing results. Therefore, special care must be taken to choose
appropriate oils for the refrigerant used for each specific system. It is important for
handling POEs to minimize the contact time with air since POEs are highly hydro-
scopic and therefore any opportunity to accummulate moisture must be avoided. As
an example, a cycle flushing procedure, when the system originally charged with
R22 is retrofitted with R407C, is explained as follows:
• Check refrigerant and oil compatibility: R22 and mineral oils are com-
patible, as are R407C and POE oils. However, R407C is not compatible
with mineral oils. Therefore, a flushing of the system is needed.
• Old refrigerant removal: Recover old refrigerant charged in the system
using a recovery machine.
• Initial oil drain from the compressor: Drain all old oil from the compressor
through the drain port of the compressor, if any is available. If no oil drain
port is available, separate the compressor from the system and drain the
oil from the compressor through the ports.
• Initial oil drain from the heat exchangers: Drain as much of the oil from
the cycle by blowing off with compressed nitrogen gas through the service
ports.
• Reassemble the compressor if it was disassembled.
• Evacuate the system using a vacuum pump.
• Fill the system with new lubricant (POE) to the minimum quantity
required and charge the system with R407C (use recovered R407C if
available).
• Run the system for approximately 10 minutes to help any residual old
refrigerant gas and oil to mix with new refrigerant and oil.
• Repeat above procedures except initial oil removal from the heat exchang-
ers until the refractive index difference between the oil sample and new
oil is within 1%.
9.4 REFRIGERANT MIXING

This section describes a generalized procedure for blending refrigerants. As an
example, the blending of R32 and R125 to make a binary mixture R410A is
explained. It should be noted that special care must be taken when blending flam-
mable refrigerants such as R32, R152a and hydrocarbons.
• Prepare two containers charged with pure components, R32 and R125,
and one empty container for the mixture. A mixture container must have
two valves, liquid and gas.
• Evacuate the empty container using a vacuum pump to remove any
remaining gas and moisture in the container.
• Calculate the total mass of the mixture to blend and its component mass.
For example, use 5 kg of R32 and 5 kg of R125 to make 10 kg of R32/R125
mixture with 50/50 wt.% mass fraction.
• Charge lower vapor pressure refrigerants first. If the higher vapor pressure
refrigerant is charged first, it may not be easy to charge the lower vapor
pressure fluid to the mixture container.
• To enhance the refrigerant transfer, place the container for the mixture in
a cold place (such as in a bucket filled with dry ice or ice water).
• Place a R125 container on the weighing scale and connect the R125
container and the mixture container with a refrigerant hose.
• While weighing the R125 container, transfer R125 to the mixture con-
tainer by adjusting container valves until the required amount of R125 is
transferred.
• Repeat the same procedure to transfer R32 from the R32 container to the
mixture container.
• Mix well by shaking.
• Take a liquid sample of the refrigerant mixture from the mixture container
and check the mass fraction of the mixture by using a gas chromatograph.
• Adjust the mass fraction. If the desired mass fraction is not achieved, then
calculate the amount to add from the measured mass fraction, add the
insufficient component and measure the mass fraction again. Repeat this
procedure until the desired mass fraction is achieved within 1%.
9.5 REFRIGERANT MASS FRACTION MEASUREMENT

Maintaining the refrigerant mass fraction for mixtures is important to guarantee
design performance, safety and reliability. The procedure used for measuring the
refrigerant mass fraction follows.
• Prepare refrigerant sample bottle. The volume of the sample bottle is sized
such that after the refrigerant sample expands into the bottle, only vapor
exists (approximately 1 l bottle is used as an example).
• Clean the sample bottles using acetone or another solvent to remove any
residual refrigerant and oil that might accumulate in the bottles: Evacuate
the bottles and pour approximately 100 ml of acetone in the bottle at
atmospheric pressure. Violently agitate the sample bottle for approxi-
mately 30 seconds. Charge nitrogen into the bottle to about 350 kPa
(nitrogen is used to rapidly push the acetone–oil solution out of the sample
bottle). Turn the bottle upside down and open the valve to allow the
acetone–oil solution to flow out.
• Evacuate the (preferably heated) sample bottle for several hours to remove
any remaining acetone.
• Attach the sample bottle to the sample tube already installed to a system
tube. The sample tube must be inserted into the middle of the refrigerant
stream in the liquid and vapor lines to ensure that bulk samples are
Sample Bottle
Upper Valve
Needle Valve
Vacuum Pump
Sample Tube
Lower Valve
System Pipe
Refrigerant Flow
FIGURE 9.5.1 Sampling refrigerant.
analyzed as shown in Figure 9.5.1. To control the sampling, it is common

practice to install either a manual valve or a solenoid valve between the
sample bottle and tube.
• Take the first refrigerant sample into the sample bottle by opening valves
and throw away to flush the sample section.
• Reconnect a new sample bottle and evacuate the sample section by using
the vacuum pump.
• Take the refrigerant sample into the sample tube by opening and closing
the lower valve. To ensure that the sample tube is filled with liquid, it
should be packed in dry ice or ice water.
• Expand the refrigerant sample from the tube into the sample bottle by
opening and closing the upper valve. The sample tube should be heated
to ensure that all refrigerant is completely evaporated.
• Remove the sample bottle from the system after closing the valves.
• Analyze the samples by using the gas chromatograph.
• Repeat the above procedure three times to ensure that the device is work-
ing properly.
9.6 EVACUATING A SYSTEM

Evacuating refrigeration and air-conditioning systems is very important to secure a
steady performance and reliability of the system since this process removes residual
noncondensable gases and moisture from the system. Evacuating can remove gases
quickly but takes longer to remove moisture from the system. POE oils are very
hydroscopic and form acids together with the moisture and refrigerant at elevated
temperature. General procedures are as follows:
FIGURE 9.6.1 Vacuum pump. (Photo courtesy of INFICON.)
• Choose the size of vacuum pump that is appropriate for the system size.
Make sure the system pressure is not higher than 1 atm and that all
refrigerant that may have been in the system is reclaimed. Figure 9.6.1
shows a typical 1/2 hp deep vacuum pump.
• Make sure the space around the pump exhaust is well ventilated since the
vacuum pump will emit residual gases from the system and sometimes
discharge oil mist.
• Connect the middle port of the manifold gauge set to the vacuum pump.
• Open both system’s service ports (liquid and gas line ports).
• Open both low and high pressure side valves of the manifold gauge set.
• Turn on the vacuum pump. Keep evacuating until the vacuum pressure
reaches 500 µm of Hg, then run the vacuum pump at least 30 minutes
more to remove moisture left in the system or dissolved in the oils. The
longer the time for evacuation and the higher the temperature of all internal
surfaces of the system, the more complete is the removal of moisture.
• Shut down procedure for vacuum: Close valve to the system to be evac-
uated, bring the inlet port pump to atmospheric pressure (open valve or
disconnect hose), then pump can be turned off.
• Vacuum pump oil change: After every 20 to 30 operation hours, the oil
of the vacuum pump must be changed as it picks up moisture and con-
tamination. Keep a service sheet for every vacuum pump where operating
hours and oil changes are recorded.
9.7 REFRIGERANT CHARGE

Refrigerant containers are different for pure and mixed refrigerants to ensure that
mixtures maintain consistent mass fractions. Containers for pure refrigerants such
as R22 and R134a have only one discharge port since charging liquid or gas does
FIGURE 9.7.1 Manifold gauge set. (Photo courtesy of INFICON.)
not make any difference. However, containers for mixtures such as R407C and
R410A have two discharge ports, a liquid port and a gas port. When charging
refrigerant mixtures to the system, the liquid port should be used to maintain the
mass fraction. Other than this precaution, the same refrigerant charging procedure
can be used for both pure refrigerants and mixtures, explained as follows:
• Determine the required refrigerant charge from the product specification

label or manual. If not found, contact the system manufacturer. If all else
fails, the degre of superheating at the evaporater outlet (or possibly sub-
cooling at the condensor outlet) can be used as a charging criterion.
However, this method is not ideal since the charging progress does not
usually occur at design conditions.
• Place a refrigerant container on the weighing scale and connect the refrig-
erant container, liquid port, system service ports and manifold gauge set
(Figure 9.7.1) with refrigerant hoses.
• Make sure the system has been evacuated. If not, evacuate the system
based on Section 9.6.
• Purge the hose and manifold gauge set if necessary (emission minimized
hoses do not need this procedure). Add a small amount of refrigerant gas
by quickly opening and closing a refrigerant container’s gas-side valve.
Release a refrigerant and air mixture in the hose by loosening and tight-
ening the refrigerant hose.
• Open a system liquid line service port.
• Start to charge liquid refrigerant to the system by opening the refrigerant
container’s liquid-side valve very slightly while the system stays off.
• Add approximately 70 to 80% of the required charge to the system in

liquid form by using the pressure difference between the refrigerant con-
tainer and the system.
• Switch the manifold gauge valve opening. Close the high pressure side
valve and open the low pressure side valve. Open a system gas line service
port. Add more refrigerant to obtain the design charge by operating the
compressor.
• If the optimal charge is uncertain, add more refrigerant until the sight
glass at the condenser outlet becomes clear, securing a degree of subcool-
ing at the condenser outlet or the desired superheating at the evaporator
outlet is obtained.
9.8 LEAK CHECKING

There are three common ways to check a system for leaks: bubble test with soap
solution, electronic leak detector and system pressure change observation.
• Charge the system with nitrogen up to the system design pressure.

• Bubble test:
• Prepare leak detection soap solution for leak testing.
• Apply soap solution to all fittings and watch carefully for bubbles.
Leak location is indicated by soap bubbles.
• This method is a useful way to find a relatively large leak.
• Electronic leak detector (Figure 9.8.1):

• Add 50 to 100 g HCFC or HFC refrigerants to the system. If available,
use the recovered refrigerant. Pressurize with nitrogen.
• Move the probe slowly around all fittings. Locate the leak point when
the leak detector signals a leak.
• This method is a useful way to find a relatively small leak.
• Pressure change observation:

• Charge nitrogen up to the desired test pressure.
• Measure the system pressure over the desired time (usually overnight).
Pressure should remain unchanged. Temperature changes of the sur-
roundings must be considered.
• This method is a useful way to find a relatively small leak.
9.9 MASS FRACTION SHIFTS

An inherent feature of zeotropic mixtures is the different boiling points of their
components that result in different vapor and liquid mass fractions at equilibrium.
As shown in Figure 9.9.1, the saturated vapor contains more low boiling point
component while the saturated liquid contains more high boiling point component
FIGURE 9.8.1 Electronic leak detector. (Photo courtesy of INFICON.)
Pressure: Constant
Dewpoint Line
Superheated
Ta Vapor
Saturated
Tsv Vapor
Two Phase
Temperature
Range
Ttp
(Tsv-Tsl):
Temperature
Glide
Tsl
Saturated
Liquid Tb
Boiling Point
Line
Subcooled
Liquid
0 Xmix,l Xmix Xmix,v 1.0

a b
Mass Fraction
FIGURE 9.9.1 Temperature–mass fraction diagram of a zeotropic mixture.

when the temperature is between its saturated liquid and vapor temperature (Tsl and
Tsv). This mass fraction difference brings new design issues:
• Mass fraction shift within the cycle.

• Mass fraction shift due to leakage.
• Mass fraction shift during refrigerant transfer between containers.
• Cycle performance effects due to the mass fraction shift.
9.9.1 MASS FRACTION SHIFT IN THE CYCLE

Two major mechanisms cause a mass fraction shift within the cycle: the use of an
accumulator due to the vapor-liquid volume fractionation effect and the differential
refrigerant solubility into the compressor lubricant. Three different investigation
efforts are introduced in this section.
To investigate this issue, Corr and Murphy (1994) developed a simplified bulk-
tank model, “Cyclops.” Figure 9.9.2 shows the refrigerant distribution in the cycle.
The compressor contains oil and refrigerant mixture in the oil sump and refrigerant
gas within the shell other than the sump. The condenser contains two-phase, super-
heated vapor and subcooled liquid refrigerant. The evaporator contains two-phase
and superheated refrigerant.
Usually the internal volume of the expansion device is negligible. When the
cycle reaches its steady state, the circulating mass fraction should be the same at
every inlet and outlet of each component. When evaporating and condensing
processes are assumed as isobaric processes, the mass fraction of the two-phase
refrigerant differs from that of the single phase refrigerants (either superheated gas
or subcooled liquid) due to the different boiling or dew points of the pure compo-
nents. If the evaporation and condensation processes are simplified as bulk-liquid
Subcooled Liquid Two-Phase Superheated Vapor
3
2'
Condenser
Expansion Circulating Compressor

Device Composition
Evaporator
Refrigerant and
4' 1 Oil Mixture
Two-Phase Superheated Vapor
FIGURE 9.9.2 Refrigerant distribution in the cycle.

and bulk-vapor, the average liquid mass fraction and the average vapor mass fraction
are different from the circulating mass fraction due to the vapor-liquid volume
fractionation. Moreover, the circulating mass fraction shifts from the charged mass
fraction because the more volatile component accumulates predominantly in the
condenser vapor phase.
Corr and Murphy (1994) assumed that the subcooled liquid mass fraction is
similar to the average saturated liquid mass fraction of the condenser and the
superheated suction vapor mass fraction is similar to the average saturated vapor
mass fraction of the evaporator. With this simplified assumption, Corr and Murphy
showed that –1 to 3% of R32 mass fraction is shifted in the circulating refrigerant
when R32/R125 (60/40 wt.%) is charged.
To illustrate the effect of mass fraction shift on the cycle performance, the
changes of volumetric capacity and coefficient of performance (COP) are calculated
when R32 mass fractions of two binary mixtures of R32/R134a (30/70 wt.%) and
R32/R125 (50/50 wt.%) are changed with 10% variation from the charged concen-
tration, as shown in Figures 9.9.3 and 9.9.4. R32/R134a (30/70 wt.%) exhibits
approximately twice larger changes in volumetric capacity and COP due to the mass
fraction shift than that of R32/R125 (50/50 wt.%). If the circulating mass fraction
15
Volumetric Capacity Changes [%]
R32/R134a (30/70 wt.%)

10
R32/R125 (50/50 wt.%)
5
−5
−10
−15
−0.1−0.08 −0.06 −0.04 −0.02 0 0.02 0.04 0.06 0.08 0.1
R32 Mass Fraction Changes
Te = 5°C, Tc = 45°C
FIGURE 9.9.3 Performance changes due to mass fraction shift (Corr and Murphy, 1994).
6
R32/R134a (30/70 wt.%)
4
R32/R125 (50/50 wt.%)
COP Changes [%]
−2
−4
−6
−0.1 −0.08 −0.06 −0.04 −0.02 0 0.02 0.04 0.06 0.08 0.1
R32 Mass Fraction Changes
Te = 5 °C,Tc = 45°C
FIGURE 9.9.4 Performance changes due to mass fraction shift (Corr and Murphy, 1994).
30
R32
25 R125
R134a
Solubility [wt. %]
20
15
10
0
−20 10 0 10 20 30 40 50
Temperature [°C]
FIGURE 9.9.5 Solubility of HFC refrigerants in ISO 32 polyol-ester (Corr and Murphy, 1994).
shift ranges 10%, R32/R134a (30/70 wt.%) undergoes volumetric capacity and COP
variation within 10% and 2%, respectively. This result is due to the larger temperature
glide of R32/R134a (30/70 wt.%), a zeotropic mixture, than that of R32/R125 (50/50
wt.%), almost an azeotropic mixture. Therefore, the mass fraction shift in the cycle
should be accounted for in the cycle design, especially for the zeotropic mixtures
with large temperature glides.
Figure 9.9.5 shows an example for the different HFC refrigerant solubility in
the ISO 32 polyolester oil (Corr and Murphy, 1994). As shown in Figure 9.9.5, the
solubility of R32 is much lower than that of R125 and R134a due to its low molecular
weight. Therefore, R32 resides in the heat exchangers or circulates through the cycle,
more so than the other components do if binary mixtures, R32/R125 or R32/R134a,
are charged. As the compressor sump temperature decreases, the difference between
the refrigerant solubility increases. Even more R32 then migrates to the heat
exchangers or circulates in the cycle. However, the impact of the different refrigerant
solubility in the oil is not so significant because for large systems, the oil charge is
usually smaller than that of the refrigerant charge and the compressor sump tem-
perature is usually high enough to maintain a lower refrigerant solubility. In small
systems such as domestic refrigerators, the oil charge can equal or exceed the
refrigerant charge and these effects are more important.
In 1995, Sumida et al. also investigated the circulating mass fraction shift of a
zeotropic mixture in the cycle. Sumida et al. distinguished between “circulating mass
fraction” on a mass flux basis from “existing mass fraction” on a mass basis, defined
as: The circulating mass fraction (α) is the ratio of the mass flux of the more volatile
component to the total mass flux of the refrigerant mixture in the cycle, as shown
in Equation 9.1. The existing mass fraction (β) is the ratio of the mass of the more
volatile component to the total mass of the refrigerant mixture in the cycle, as shown
in Equation 9.2.
wl (1 − fv )ρl ul + wv fvρvuv
α= (9.1)
(1 − fv )ρl ul + fvρvuv
wl (1 − fv )ρl + wv fvρv
β= (9.2)
(1 − fv )ρl + fvρv
where
w = local mass fraction of the more volatile component
ρ = density
u = mean velocity
fg = void fraction
By introducing the following nondimensional ratios — gas-liquid area ratio (F),

gas-liquid density ratio (D), and gas-liquid slip ratio (S) — α and β can be expressed
as Equations 9.3 through 9.7.
F = fv /(1 − fv ) (9.3)
D = ρv /ρl (9.4)
S = uv /ul (9.5)
wl + wv FDS
α= (9.6)
1 + FDS
wl + wv FD
β= (9.7)
1 + FD
If δ is defined as the mass fraction difference between the circulating mass

fraction and existing mass fraction, δ can be expressed as Equation 9.8,
FD(S − 1)( wg − wl )
δ = α −β = (9.8)
(1 + FDS )(1 + FD)
Therefore, the circulating mass fraction is different from the existing mass
fraction except in the case of either a zero slip between gas and liquid or the same
liquid and vapor mass fraction. Since two-phase flow of any fluid has a positive slip
ratio and since zeotropic mixtures have a higher gas mass fraction than liquid mass
fraction, the mass fraction difference δ always becomes positive for the two-phase
flow of a zeotropic mixture.
Consider the mass fraction difference between the charged mass fraction (γ) and
the circulating mass fraction (α). From the mass conservation of the more volatile
component in the total cycle, γ can be expressed in terms of β as shown in Equation 9.9,
γWtotal = ∑ (β W )i i (9.9)
If φ is defined as the mass fraction difference between the circulating mass

fraction and charged mass fraction, φ can be expressed in terms of δ as shown in
Equation 9.10 by rearranging Equation 9.9 with Equation 9.8,
 
φ=α−γ = ∑  δ WW
i
i
i

total 
(9.10)
To determine the mass fraction difference between the circulating mass fraction
and charged mass fraction φ, the mass fraction difference between the circulating
mass fraction and existing mass fraction δ must be determined for each component.
However, δ for single phase becomes zero because of zero slip; therefore, only the
contribution of the two-phase components remains. From the void fraction correla-
tion for fg, parameters F and S are determined from the Equations 9.3 and 9.11,
1 − fv
S= (9.11)
fv (1/x − 1)(ρv /ρl )
Sumida et al. used Smith’s correlation for void fraction and showed that the
circulating mass fraction of R32/134a (30/70 wt.%) shifts from 0.32 to 0.42, depend-
ing on the amount of refrigerant in the accumulator. They also showed that the
capacity is affected up to 10% because of this mass fraction shift; however, the COP
is maintained.
In another study of this issue, Chen and Kruse (1995) also investigated the
circulation mass fraction shift. Chen and Kruse recommended Highmark’s void
fraction model after comparing seven different void fraction models with their
experiment. Chen and Kruse examined the mass fraction shift of R23/R152a (20/80
and 25/75 wt.%) and found the mass fraction shifts of 0.06 and 0.05 for each mass
fraction. Chen and Kruse also showed the mass fraction shifts and their performance
effects for three additional refrigerant mixtures, as shown in Table 9.1.
TABLE 9.1
Mass Fraction Shift and Capacity Changes of Three Refrigerant Mixtures
Refrigerant Mixture Mass Fraction Shift [wt.%] Capacity Changes
R407C (R32/R125/R134a, R32: +1.5, R125: +1.4, R134a: –3.2 +0.9%

23/25/52 wt.%)
R32/R134a (30/70 wt.%) R32: +3.0, R134a: –3.0 +1.1%
R404A (R125/R143a, 44/52 wt.%) R125: +0.1, R143a: +0.1, R134a: –0.2 +0.03%
Source: Chen and Kruse, 1995.

xi,l (1- xq)+ xi,v (xq)
Vapor: n i,l x i,l
Liquid: n i,v x i,v
Liq
eak
uid
rL
po
Le
Va
ak
xi,l (1-xq)+xi,v (xq-Rleak ) x i,l (1-xq){1-Rleak /(1-xq)} + xi,v xq
1 - R leak 1 - R leak
Vapor: n i,l x i,l Vapor: n i,l x i,l

xi,v Rleak
Liquid: n i,v x i,v Liquid: ni,v x i,v
xi,l R
leak
FIGURE 9.9.6 Refrigerant leakage model (Kim and Didion, 1995a).
9.9.2 MASS FRACTION SHIFT DUE TO LEAKAGE

The simplest and biggest problem of the refrigeration and air-conditioning equipment
is a refrigerant leak from refrigerant tanks or refrigeration systems. In the past, the
system has been simply charged again or refilled on site by adjusting charge to
obtain the desired operating pressures in the presence of a leak. However, this method
of recharging needs to be reexamined especially when the system uses refrigerant
mixtures because of the mass fraction shift. Refrigerant leaks can be divided into a
vapor leak and liquid leak, as shown in Figure 9.9.6. Typically, the vapor leak is a
slow process of losing refrigerant since the vapor density is much lower than that
of liquid. Therefore, the vapor leak can be assumed as an isothermal leak process
since the refrigerant remaining in the refrigerant tank or refrigeration system can
exchange heat with the ambient and maintain a constant temperature. The liquid
leak is a fast process of losing refrigerant and can be assumed as an adiabatic leak
process since the temperature of the refrigerant remaining in the refrigerant tank or
refrigeration system can drop quickly without exchanging heat with the ambient.
Isothermal vapor leaks and adiabatic liquid leaks can be modeled based on the
following assumptions:
• Refrigerant mixture is in a thermodynamic equilibrium condition.

• Only one phase of refrigerants leaks.
• Mass fraction of leaking refrigerant is the same as that of the phase that
is leaking.
Liquid and vapor are assumed initially in thermodynamic equilibrium. If xl, xv

and xq are defined as the mass faction of the liquid phase, mass faction of the vapor
phase and overall vapor mass quality, the overall mass fraction of the i-th component
in the tank or system can be expressed as Equation 9.12,
xi = xl ,i (1 − xq ) + xv,i xq (9.12)
Consider the vapor leak by introducing a nondimensional parameter, leakage rate

(Rleak), defined as the mass fraction of leaking vapor to the total mass. The new
overall mass fraction of the i-th component in the tank or system can then be
expressed as Equation 9.13,
xl ,i (1 − xq ) + xv ,i x q (1 − Rleak /x q )
xi ,new = (9.13)
1 − Rleak
Therefore, the change of the overall mass fraction of the i-th component in the tank
or system can be expressed as Equation 9.14,
Rleak
∆xi = xi ,new − xi = (1 − x q )( xl ,i − x v ,i ) (9.14)
1 − Rleak
Similarly, if there is a liquid leak, the change of the overall mass fraction of the i-th
component in the tank or system can be expressed as Equation 9.15,
Rleak
∆xi = xi ,new − xi = x q ( x v ,i − xl ,i ) (9.15)
1 − Rleak
The isothermal vapor leak is of more concern than the liquid leak because it
occurs for a longer period of time and sometimes is harder to detect; therefore, a
partial recharging may be considered after the vapor leak. If there is a liquid leak,
it occurs over a short period of time and the loss of total refrigerant is significant;
therefore, a complete recharging may be considered after a liquid leak. However,
the isothermal vapor leak also needs to be treated carefully when the components
of the mixture have a large vapor pressure difference because the mass fraction shift
becomes the issue in this case.
Kim and Didion (1995a) developed a leakage simulation model, REFLEAK,
using the approach described above. Figure 9.9.7 shows the simulation results of an
isothermal vapor leak cases for the selected refrigerants R410A, R32/R125 (30/70
wt.%) and R407C by using REFLEAK. The boiling points of R32, R125, and R134a
are –51.7, –48.1, and –26.1˚C, respectively. As shown in Figure 9.9.7, the mass
fraction of the more volatile component decreases and the mass fraction of the less
volatile component increases as a result of a vapor leak. If there is 50% vapor lost,
R410A loses 2% of R32 liquid and 1% of R32 vapor. For the same case, R32/R125
(30/70 wt.%) loses 2% of R32 liquid and vapor and R407C loses 7% of R32 liquid
and vapor. Therefore, the impact of the vapor leak will be more severe for R407C
and the next one is R32/R125 (30/70 wt.%). R410A has the least impact.
Bivens et al. (1996) also developed a similar model by integrating the differential
equations for mass fraction shifts and obtained a similar result as Kim and Didion.
0.60
Tamb = 30°C, xq =0.5
R32 Liquid R32, Vapor
0.55 R125 Liquid R125 Vapor

Mass fraction
0.50
0.45
0.40
0 20 40 60 80 100
Leakage Rate [%]
(a) R410A
1.0
Tamb = 30°C,xq =0.5
R32 Liquid R32, Vapor
0.8
R134a Liquid R134a Vapor
Mass fraction
0.6
0.4
0.2
0.0
0 20 40 60 80 100
Leakage Rate [%]
(b) R32/125 (30/70 wt.%)
1.0
0.9 R32 Liquid R32, Vapor Tamb = 30°C, xq =0.5
0.8 R125 Liquid R125 Vapor
0.7
R134a Liquid R134a Vapor
Mass fraction
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 20 40 60 80 100
Leakage Rate [%]
(c) R407C
FIGURE 9.9.7 Isothermal vapor leak process (Kim and Didion, 1995b).
TABLE 9.2
Mass Fraction Shift during Liquid Charging from
Container (25˚C)
R410A R407C
Liquid Level [%] R32 R125 R32 R125 R134a
85 49.50 50.50 23.0 25.0 52.0

50 49.42 50.58 22.8 24.9 52.3
40 49.39 50.61 22.7 24.8 52.5
30 49.35 50.65 22.6 24.7 52.7
20 49.30 50.70 22.5 24.6 52.9
15 49.26 50.74 22.3 24.6 53.1
10 49.20 50.80 22.2 24.5 53.3
5 49.15 50.85 22.0 24.4 53.6
2 49.10 50.90 21.9 24.2 53.9
Source: Bivens and Yokozeki, 1998.
9.9.3 MASS FRACTION SHIFT DURING CONTAINER TRANSFERS

In general, refrigerants undergo a couple of transportation steps between containers
before they are charged to the final system. While being transferred, there is a
potential mass fraction shift. When charging refrigerant mixtures, it is important to
charge from the liquid port of the storage container to minimize any mass fraction
shift. Therefore, emptying and refilling a container can be regarded as the same
process as that of an adiabatic liquid leak. Bivens and Yokozeki (1998) examined
this issue in detail by using the model they developed previously.
Table 9.2 shows mass fraction shifts of two mixtures while the container is being
emptied from 100% liquid to 2% liquid. As can be seen from Table 9.2, the maximum
charging mass fraction shift (the mass fraction of the mixture that is actually charged
to a refrigeration system from the container) is 0.4% of R32 and R125 for R410A
and 1.9% of R134a for R407C.
REFERENCES
Air-Conditioning and Refrigeration Institute, 1994, Applicant Study Guide for Refrigerant
Containment, Section 608, Clean Air Act, 2nd Edition.
Bivens, D.B., M.B. Shiflett, C.C. Allgood and A. Yokozeki, 1996, “Zeotropic Mixture Sepa-
rations Analyses,” Proceedings of the 1996 International Refrigeration Conference at
Purdue, West Lafayette, IN, pp. 113–118.
Bivens, D.B. and A. Yokozeki, 1998, “Mass Fraction Changes during Container Transfers for
Multi-component Refrigerants,” Proceedings of the 1998 International Refrigeration
Conference at Purdue, West Lafayette, IN, pp. 81–86.
Chen, J. and H. Kruse, 1995, “Calculating Circulation Concentration of Zeotropic Refrigerant
Mixtures,” International Journal of HVAC&R Research, Vol. 1, No. 3, pp. 219–231.
Chen, J. and H. Kruse, 1997, “Concentration Shift Simulation for the Mixed Refrigerants
R404A, R32/134a, and R407C in an Air-Conditioning System,” International Journal
of HVAC&R Research, Vol. 3, No. 2, pp. 149–157.
Corr, S. and F.T. Murphy, 1994, “Mass Fraction Shifts of Zeotropic HFC Refrigerants in
Service,” Proceedings of IIR Conference for CFCs, The Day After, pp. 29–40.
Kim, M.S. and D.A. Didion, 1995a, “Simulation of Isothermal and Adiabatic Leak Processes
of Zeotropic Refrigerant Mixtures,” International Journal of HVAC&R Research, Vol.
1, No. 1, pp. 3–20.
Kim, M.S. and D.A. Didion, 1995b, “Simulation of a Leak/Recharge Process of Refrigerant
Mixtures,” International Journal of HVAC&R Research, Vol. 1, No. 3, pp. 242–254.
Sumida, Y., N. Tanaka and T. Okazaki, 1995, “Prediction of the Circulating Mass fraction of
a Zeotropic Mixture in a Refrigerant Cycle,” Proceedings of 19th International Con-
gress of Refrigeration, Vol. IVb, pp. 1013–1020.

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Vapor

Boca Raton London New York Singapore

© 2005 by Taylor & Francis Group, LLC

Library of Congress Cataloging-in-Publication Data

Visit the Taylor & Francis Web site at

Dr. Reinhard Radermacher is a professor of mechanical engineering at the Uni-

Chapter 2 Properties of Working Fluids.............................................................17

Chapter 3 Vapor Compression Cycle Fundamentals..........................................65

Chapter 4 Methods for Improving the Cycle Efficiency..................................135

Chapter 6 Refrigerant Mixtures in Refrigeration Applications........................209

Chapter 7 Refrigerant Mixtures in Heat Pump Applications...........................221

Chapter 8 Heat Transfer of Refrigerant Mixtures ............................................237

Chapter 9 Operational Issues ............................................................................279

1.1 HEAT PUMPING

∑ QT = 0 for reversible processes

and using Equation 1.3,

After rearranging the terms, we find

1.2 OVERVIEW OF CURRENT PRODUCTS

1.2.1 RESIDENTIAL AIR CONDITIONERS AND HEAT PUMPS

1.2.2 COMMERCIAL AIR-CONDITIONING SYSTEMS

1.2.3 INDUSTRIAL SYSTEMS

1.2.4 REFRIGERATION SYSTEMS

1.3 HISTORY OF WORKING FLUIDS

1830s Caoutchoucine Distillate of india rubber

1.4 REQUIREMENTS FOR WORKING FLUIDS

• Lack of corrosion, chemically inert. Refrigerants should not corrode any

1.5 BACKGROUND OF ENVIRONMENTAL CONCERNS

1.5.2 IMPACT OF GLOBAL WARMING

Freeze 35% 65% 90% 99.5% 100%

1.5.3 INTERNATIONAL EFFORTS ON ENVIRONMENTAL PROTECTION

1.5.4 IMPACT OF ENVIRONMENTAL ISSUES ON U.S. CLIMATE

1.5.5 MIXTURES AS R22 REPLACEMENTS

Air-conditioning and Refrigeration Institute (ARI) started the R22 Alternative

2.1 THERMODYNAMIC DIAGRAMS OF PURE

mass of one component [kg]

2.1.1 TEMPERATURE-MASS FRACTION DIAGRAM

TR134a Superheated vapor

FIGURE 2.1.1 Temperature-mass fraction diagram for R32/R134a.

FIGURE 2.1.2 Evaporation process of R32/R134a.

To demonstrate the use of the diagram, a slow (equilibrium) evaporation process

m3″ + m3′ = m2′ (2.2)

and the mass balance for one component (here R32)

m3″ x3″ + m3′ x3′ = m2 x2′ (2.3)

After elimination of m3′, the vapor quality is obtained as:

m3′′ ( x2′ − x3′ )

FIGURE 2.1.3 Temperature-mass fraction diagrams with constituents of varying differences

This is a consequence of two characteristics: The boiling points of the pure

−48.0 Bubble line

FIGURE 2.1.6 T-x diagram for azeotrope R507A (P = 0.1 MPa).

FIGURE 2.1.7 T-x diagram for azeotrope R507A (P = 1 MPa).

2.1.2 PRESSURE-TEMPERATURE DIAGRAM

© 2005 by Taylor & Francis Group, LLC

FIGURE 2.1.9 Vapor pressure curves on a ln(P)-T diagram.

© 2005 by Taylor & Francis Group, LLC

FIGURE 2.1.11 ln(P)-(–1/T) diagram for R32/R134a.

© 2005 by Taylor & Francis Group, LLC

2.1.3 PRESSURE-ENTHALPY DIAGRAM

© 2005 by Taylor & Francis Group, LLC

© 2005 by Taylor & Francis Group, LLC