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WET COMPRESSION VERSUS DRY COMPRESSION IN
REFRIGERATION CYCLES WORKING WITH PURE OR NON-

AZEOTROPIC REFRIGERANT MIXTURES FOR AIR-
' CONINTIONERS
by
WAYNE SWANEPOEL
submitted in partial fulfilment of the
requirements for the degree
MAGISTER INGENERIAE
in
MECHANICAL ENGINEERING
in the
FACULTY OF ENGINEERING
at the
RAND AFRIKAANS UNIVERSITY
STUDY LEADER: PROF J.P. MEYER
OCTOBER 1998
ABSTRACT
Wet compression versus dry compression in refrigeration cycles working with

pure refrigerants or non-azeotropic mixtures is investigated in this paper. In
total 34 pure refrigerants as well as 31 non-azeotropic binary mixtures are
considered. This resulted in approximately 300 different mixtures being
analysed. The pure refrigerants and refrigerant mixtures were analysed for one
cooling application, namely that of spatial air conditioning at an evaporating
temperature of 7°C, and a condensing temperature of 50°C. The investigation
was conducted with cycle analyses calculating performances at different wet and
dry compressor inlet values. Use was made of thermodynamic refrigerant
properties calculated from a computer database. It was concluded that for both
pure and non-azeotropic refrigerants analysed, all those with re-entrant
saturation vapour lines produce better cooling COP's when the refrigerant is
superheated before entering the compressor. Only a few of the refrigerants with
bell-shaped T-s curves consistently produce higher cooling COP's when wet
compression is used. However, their cooling capacities decreased while the
compressor displacement rates increased. It was concluded that in general dry
compression is more favourable than wet compression. From the exceptions that
do exist, some manage to produce relatively high COP c 's while retaining
competitive cooling capacities. A by-product of this study is that, from the vast
amount of refrigerant mixtures analysed, valuable knowledge was gathered
regarding refrigerants not commonly used in the applications considered.
Keywords:
refrigeration cycles
refrigerant mixture
pure refrigerants
non-azeotropic refrigerants
binary
wet compression
dry compression
ii
ACKNOWLEDGEMENTS
A special word of thanks to my wife for her emotional support during this research period.
I would like to thank Prof. J.P. Meyer for his professional guidance and support during this
exciting period.
Thank you for the financial support provided by the FRD and ESCOM.
ifi
CONTRIBUTIONS OF THIS STUDY
A total of 34 pure refrigerants were analysed for a commonly known

refrigeration cycle used in practise: the cooling of space due to air
conditioning.
A total of 31 binary non-azeotropic refrigerant mixtures were analysed at

mass ratio intervals of 0.1 for the same application mentioned above.
In both the evaluations of pure refrigerants and non-azeotropic mixtures, the

refrigerants were evaluated on the bases of cooling COP, cooling capacity
and compressor displacement. This enabled the identification of high
performing refrigerants.
The following conclusions were made:
• The top performing non-azeotropic mixtures produce higher COP G 's than
the top performing pure refrigerants. It should be kept in mind, however,
that this conclusion is based on the method of comparison between non-
azeotropes and pure refrigerants chosen for this study. The chosen method
of comparison for this study is summarised in Figure I. Viewing Figure I,
it can be seen that the evaporation and condensation temperatures chosen
for the evaluation of a pure refrigerant, are retained as respectively
bubble point and dew point temperatures for the evaluation of the non-
azeotropic mixture. Other methods of comparison may lead to different
results.
Tcond
Pure refrigerant
Non-azeotrove
Tevap
Figure I A comparison between the evaporation and condensation temperatures of a pure

refrigerant, and the bubble point and dew point temperatures of a non-azeotropic mixture
iv
The top performing refrigerants are summarised in Tables I and II. In both
the tables the non-azeotropic mixtures were divided into three categories
according to the amount of temperature glide displayed by each of them. A
"low temperature glide" is defined by a refrigerant having a temperature
glide that lies between 0°C and 5°C. A "medium temperature glide" is
defined by a refrigerant having a temperature glide that lies between 5°C and
10°C. A refrigerant that has a temperature glide higher than 10°C falls in the
"high temperature glide" category. All the refrigerants were divided into
groups of "phased-out", "temporarily acceptable" and "acceptable"
refrigerants. These three groups correspond to the groups identified by the
Montreal Protocol: "phased-out" refrigerants being CFC's or similar
refrigerants phased-out since January 1996, "temporarily acceptable"
refrigerants being HCFC's or similar refrigerants that will be phased-out in
future under the Montreal Protocol, and "acceptable" refrigerants being thoSe
deemed acceptable for use in future. The phased-out refrigerants are analysed
but omitted here for obvious reasons, while Table I lists the temporarily
acceptable refrigerant mixtures and Table II shows the acceptable refrigerant
mixtures.
Temporarily acceptable refrigerant mixtures

Low Temperature Glide Medium Temperature Glide High Temperature Glide
(0°C-5°C) (5°C-10°C) (>10°C)
R22/R134a 4.890(0.9) R22/R142b 6.056(20SH) R123/R134a 14.07(10SH)
(0.7/0.3) 123.8 (0.3/0.7) 195.4 (0.6/0.4) 191.4
1.15 0.295 9.97 0.368 26.98 0.44
R22/R124 4.887(0.9) R22/R142b 5.880(0.9) R123/11134a 13.24(10SH)
(0.1/0.9) 103.1 (0.6/0.4) 153.4 (0.8/0.2) 185.3
4.45 0.539 _ 9.01 0.291 25.26 0.614
Table I The highest COP, values for each of the three levels of temperature
glides, considering only temporarily acceptable refrigerant mixtures. The first
value in each block is the COP, (with the relevant inlet vapour quality in
brackets), the second is the specific cooling capacity (kJ/kg) and the third is the
compressor displacement per kilowatt cooling (litre/s)
Acceptable refrigerant mixtures

(0°C-5°C) (5°C-10°C) (>10°C)
R218/RC318 5.96(20SH) R143/R143a 6.588(0.9) R32/R143 13.0(0.8)
(0.9/0.1) 60.9 (0.9/0.1) 215.9 (0.3/0.7) 238.1
2.78 0.398 9.94 0.611 25.85 0.235
R125/R143a 5.087(20SH) R125/R143 5.873(1.0) R32/R143 12.69(1.0)
(0.8/0.2) 103.1 (0.1/0.9) 239.6 (0.4/0.6) 308.0
0.08 0.238 9.64 0.615 26.42 0.198
Table II The highest COP, values for each of the three levels of temperature
glides, considering only acceptable refrigerant mixtures. The first value in each
block is the COP, (with the relevant inlet vapour quality in brackets), the
second is the specific cooling capacity (kJ/kg) and the third is the compressor
displacement per kilowatt cooling (litre/s)
V
4. The refrigerants evaluated were evaluated for both wet and dry compression
processes. This resulted in the identification of refrigerants susceptible to
the advantages of wet compression.
The following conclusions were made:
All the refrigerants, pure and non-azeotropic, could be divided into

two groups according to their T-s graphs (temperature-entropy graphs).
Two shapes were identified: those with bell-shaped curves as in Figure
II and those with re-entrant saturated vapour lines as in Figure III.
120°C
cc?
E.' 50°C Condens in
7°C Evaporating
gr-
-70°C
Entropy [kJ/kg.K] Entropy [kJ/Icg.K]
Figure II The T-s graph of NH3 as an example Figure III The T-s graph of RC318 as an
of a bell- shaped curve example of a curve with a re- entrant
saturated vapour line
From the pure refrigerants with bell-shaped T-s graphs, only R32 and
NH3 produce higher COP c 's when wet compression is used. Wet
compression, however, reduces the cooling capacity and increases the
compressor displacement.
The majority of non-azeotropic mixtures belong to the family with

bell-shaped curves. As was found with pure refrigerants, none of the
mixtures with re-entrant saturation vapour line on the T-s curve
produce better results with the use of wet compression. The only
mixtures that respond favourably to wet compression, come out of the
bell-shaped T-s curve family. Again, wet compression reduces the
cooling capacity and increases the compressor displacement.
Non-azeotropic refrigerant mixtures tend to gain more from wet

compression than pure refrigerants.
vi
TABLE OF CONTENTS
ABSTRACT
ACKNOWLEDGEMENTS ii
CONTRIBUTIONS OF THIS STUDY iii
TABLE OF CONTENTS vi
LIST OF FIGURES viii
LIST OF TABLES iz
NOMENCLATURE x
INTRODUCTION 2
1.1 BACKGROUND 2
1.2 PREVIOUS WORK 5
1.3 PURPOSE OF THIS STUDY 5
1.4 SCOPE OF THIS STUDY 6
PART I: PURE REFRIGERANTS 8

2.1 INTRODUCTION 8
2.2 CYCLE ANALYSES 8
2.3 RESULTS 10
2.3.1 PERFORMANCE 11
2.3.2 SUMMARY OF RESULTS 13
2.3.3 T-s CURVE 17
2.3.4 CONCLUSION 19
PART II: NON-AZEOTROPIC REFRIGERANT MIXTURES 21

3.1 INTRODUCTION 21
3.2 CYCLE ANALYSES 21
3.3 RESULTS 22
3.3.1 TEMPERATURE GLIDE 48
3.3.2 T-s CURVE 54
3.3.3 DISCHARGE TEMPERATURE 55
3.3.4 CONCLUSIONS 55
vii
3.4 ENVIROMENTAL IMPACT 56

3.4.1 BEST PERFORMERS 56
3.4.2 WHAT ABOUT R123? 59
3.4.3 FLAMMABILITY AND TOXICITY 59
4. SUMMARY, CONCLUSIONS AND RECOMMENDATION 62

4.1 SUMMARY 62
4.2 CONCLUSIONS .62
4.3 RECOMMENDATIONS 64
REFERENCES 66
VIII
LIST OF FIGURES
Figure 1 Vapour-compression cycle for an (a) azeotropic and (b) non-azeotropic refrigerant
Figure 2 Vapour-compresion cycle for wet (1' to 2') and dry (1 to 2) compression for a (a)
pure refrigerant and a (b) non-azeotropic refrigerant mixture
Figure 3 The COP, results for air conditioning, using E245, R143 and NH 3
Figure 4 The specific cooling capacity results for air conditioning, using E245, R143 and NH3
Figure 5 The amount of refrigerant circulated for each kilowatt of air cooling using E245, R143
and NH3
Figure 6 The compressor displacement rate for each kilowatt of air cooling using E245, R143
and NH3
Figure 7 The T-s graph of NH 3 as an example of a bell- shaped curve
Figure 8 The T-s graph of RC318 as an example of a curve with a re- entrant saturated vapour
line
Figure 9 A comparison between the evaporation and condensation temperatures of a pure
refrigerant, and the bubble point and dew point temperatures of a non-azeotropic
mixture
Figure 10 Graph showing the discontinuity in the calculation of the COP, values for
R13b1/R152a (0.9/0.1)
Figure 11The compressor displacement and refrigerant circulated per kilowatt of cooling for
R32/R143 (0.3/0.7)
Figure 12The COP, values for R32/R143 (0.3/0.7)
Figure 13The specific cooling capacity and specific work for R32/R143 (0.3/0.7)
Figure 14 The COP, plotted as a function of the corresponding temperature glide for all the non-
azeotropes considered
Figuie 15The temperature glide distribution for R13b1/R152a
Figure 16The temperature glide distribution for R32/R142b
Figure 17The temperature glide distribution for R22/R218
ix
LIST OF TABLES
Table 1 List of pure refrigerants analysed for spatial air conditioning applications
Table 2 A summary of the maximum COP c values obtained through calculation for every pure
refrigerant. Also tabulated are the corresponding specific cooling capacity (kJ/kg) and
compressor displacement (Us) per kilowatt of cooling. These values are compared with
the values obtained at 10°C superheat, since it is commonly found in practise that the
refrigerant is compressed at this superheated value
Table 3 A list of pure refrigerants where higher COP c values were obtained by using wet
compression over dry compression. Also tabulated are the changes in COP O, specific
cooling capacity and compressor displacement values relative to the values at 10°C
superheated. A negative value indicates a decrease when wet compression is used
Table 4 The considered pure refrigerants are divided into two groups: Those refrigerants with a
bell- shaped T-s curve (refer to Figure 7); and those refrigerants with a T-s curve with a
re- entrant saturated vapour line (refer to Figure 8).
Table 5 A list of the refrigerant mixtures analysed
Table 6 A summary of the maximum COP c and corresponding specific cooling capacity (kJ/kg)
and compressor displacement (Us) per kilowatt of cooling. Also tabulated are the same
values obtained at 10°C superheat
Table 7 The top 10 refrigerant mixtures with the highest percentage improvement in COP c
obtained by using wet compression over dry compression. Also tabulated are the
changes in COPc, specific cooling capacity and compressor displacement values
relative to the values at 10°C superheated as a percentage
Table 8 The top 30 list for the highest COPc's and at what vapour quality this was achieved
Table 9 The top 30 list for the highest COPc 's for air conditioning for each of the three levels of
temperature glides.
Table 10 Table showing the three categories of refrigerant mixtures of Table 8 identified in the
light of the environmental restrictions
Table 11 The highest COP c 's for air conditioning for each of the three levels of temperature
glides. Only temporarily acceptable refrigerant mixtures are considered. The first value
is the COPc (with the relevant inlet vapour quality in brackets), the second is the
specific cooling capacity (kJ/kg) and the third is the compressor displacement per
kilowatt cooling (litre/s).
Table 12 The highest COP c 's for air conditioning for each of the three levels of temperature
glides. Only acceptable refrigerant mixtures are considered. The first value is the COP.
(with the relevant inlet vapour quality in brackets), the second is the specific cooling
capacity (kJ/kg) and the third is the compressor displacement per kilowatt cooling
(litre/s).
NOMENCLATURE
COPe Coefficient of performance for cooling
h Specific enthalpy (J kg -I )
hf Specific enthalpy at saturated liquid qualities (J kg -I )
hg Specific enthalpy at saturated vapour qualities (J kg -I )
Refrigerant mass flow for each kilowatt of cooling (kg s -I )
q Specific cooling capacity (J kg -I )
s Specific entropy (J kg -1 K -I ) or isentropic point in figures
Tcond Condensation temperature (K)
Tevap Evaporation temperature (K)
Tg TeMperature glide (K)
V Compressor displacement rate for each kilowatt of cooling (m 3 s-1)
w Specific work (J kg -I )
x Vapour quality
p Refrigerant density (kg m 3 )
Tic Compressor isentropic efficiency

CHAPTER ONE
2
1. INTRODUCTION
1.1 BACKGROUND
The Montreal Protocol is an international agreement designed to protect the

stratospheric ozone layer against substances that deplete the ozone layer. The
treaty was originally signed in 1987 and substantially amended a few times.
Since signing the Montreal Protocol new refrigerants have appeared on the
market and refrigeration equipment efficiencies have increased significantly.
Although much doubt was expressed by researchers and engineers, the causes of
ozone depletion have been accepted, and more than 160 nations have agreed on a
corrective course. The result, says Rowland', is that the ozone depletion
observed in the past twenty years should slowly decrease, barring natural
disasters such as volcanic eruptions.
The Montreal Protocol stipulates that the production and consumption of

compounds that deplete the ozone layer in the stratosphere, are to be phased out
by the year 2000. Such compounds are chlorofluorocarbons (CFC's), carbon
tetrachloride and methyl chloroform (2005 for methyl chloroform). Scientific
theory and evidence suggest that these compounds could significantly deplete
the stratospheric ozone layer that shields the planet from damaging UV-B
radiation once emitted to the atmosphere.
The Montreal Protocol was the dawn of a new age for industries, including the
air conditioning and refrigerating industry which were consuming and producing
these compounds. Short to medium term alternatives (HCFC's) were almost
readily available, but the industry was continuously faced with the challenge of
finding suitable replacements for ozone depleting compounds. Although
numerous studies have revealed various possibilities, the search for a more
efficient, cheaper and safer refrigerant is a never-ending one. The reason for
this statement is partly due to the fact that, although refrigerants are used in a
pure state, research revealed that mixtures of refrigerants can reveal some
interesting results as well. This provides an extra degree of freedom and
literally thousands of new refrigerants can be "formed". Since the advent of the
Montreal Protocol, much work has been done in an attempt to find replacements
for CFC's. These include studies on pure refrigerants, as well as mixtures of
refrigerants (see i.e. References 2 to 12).
These refrigerants can be divided into two main groups, azeotropes and non-
azeotropes. The major difference between the two groups can best be explained
by referring to Figure 1. The standard vapour-compression cycles for the two
different groups of refrigerants are presented for negligible pressure drop. The
main difference, as can be seen in the figure, lies in the region underneath the
saturation curve. This coincides with the condensing (points 2' to 3) and
evaporating processes at constant pressure (points 4 to 1) in Figure 1. These
two processes are isotropic (at constant temperature) for the azeotropes
underneath the saturation curve, as is shown in Figure la.
Evaporation and condensation of a non-azeotropic mixture takes place at non-

constant temperature, unlike that of the pure refrigerants at constant pressure. A
mixture of two refrigerants leads to a supplementary degree of freedom in
refrigeration systems during evaporation and condensation. A pure refrigerant in
the two-phase region has only one degree of freedom: the temperature is a
function of the pressure only. A non-azeotropic mixture possesses two degrees
of freedom: the temperature is a function of both the pressure and of the liquid
concentration. For this reason, when using non-azeotropes, the exchanging of
heat coincides with a drop in temperature at a constant pressure as shown in
Figure lb. Due to the fact that the different parts of the mixtures exhibit
different evaporating and condensing temperatures, this temperature glide is
common among mixtures of refrigerants.
Figure 1 Vapour-compression cycle for an (a) azeotropic and (b) non-azeotropic refrigerant
The compression process 13 , 1' to 2', in Figure 2 is called wet compression

because the entire process occurs in the mixture region with droplets of liquid
present. Several factors discourage the practise of wet compression when a
reciprocating compressor is used. One disadvantage is that the liquid
refrigerant may be trapped in the head of the cylinder by the rising piston,
possibly damaging the valves or the cylinder head. The end of the compression
process shown at point 2' in Figure 2, is saturated vapour and should thus be
free from liquid, but such is not the actual case. During compression the
droplets of liquid are vaporised by an internal heat transfer process which
requires a finite amount of time. High-speed compressors are susceptible to
damage by liquid because of the short time available for heat transfer. In a
compressor that have a rotating speed of 1800 rpm, for example, the
compression takes place at 1/60 of a second. Point 2' on the saturated-vapour
line, at the end of compression, represents only average conditions of a mixture
of superheated vapour and liquid.
4
Another possible danger of wet compression that accelerates wear, is that the
droplets of liquid may wash the lubricating oil from the walls of the cylinder.
Although wet compression is therefore likely to damage compressors that are
currently used in industry, advancements are made rapidly in materials,
lubricants and new types of compressors. It would therefore not be farfetched to
hope that wet compression might be a practical reality in the near future.
Figure 2 Vapour-compression cycle for wet (1' to 2') and dry (1 to 2) compression for a (a)
pure refrigerant and a (b) non-azeotropic refrigerant mixture
Because of the current practical problems with wet compression, dry

compression is preferable to wet compression at the present moment in time.
Points 1 to 2 in Figure 2 represent dry compression, which takes place with no
droplets of liquid present. The refrigerant that is compressed via a dry
compression process, ends up in a superheated phase. A cycle using dry
compression is called the Rankine cycle and this has been the norm for vapour-
compiession cycles up to date. The advantages are obvious if one recognises
that wet compression brings the Rankine cycle closer to the ideal Carnot cycle
for pure refrigerants and closer to the Lorentz cycle for non-azeotropic
refrigerants. For thermodynamic cycles operating between two temperatures, the
these cycles offer the highest possible efficiencies.
5
1.2 PREVIOUS WORK
Itard 14 investigated wet compression versus dry compression in heat pumps

working with pure refrigerants or non-azeotropic mixtures. From his study he
found that the principle of wet compression seems attractive to pure
refrigerants, but particularly attractive to non-azeotropic refrigerants. Only
three pure refrigerants were considered, namely: R12, R123 and NH3. Non-
azeotropic refrigerants were limited to NH3/H20 on a mass ratio of 80%/20%.
An example is given in one of the case studies considered by Itard 14 , where wet
compression could increase the COP from 69.3% to 94.8%! The results of Itard 14
are therefor exciting. However, one should not forget that only four refrigerants
(three pure and one non-azeotropic) of all the possible pure refrigerants and
non-azeotropic mixtures available on the market, were considered. Only one
heat pump application is considered in the paper of Itard 14 , namely at an
evaporating temperature of 10°C and a condensing temperature of 60°C.
1.3 PURPOSE OF THIS STUDY
It is the purpose of this paper to consider more refrigerants- 34 pure refrigerants

as well as 31 non-azeotropic binary mixtures at different concentrations. One
cooling application is considered in this paper, namely that of spatial air
conditioning at an evaporating temperature of 7°C, and a condensing
temperature of 50°C. These temperatures represent typical evaporation and
condensing temperatures used in practice. The non-azeotropic mixtures were
analysed using a dew point temperature of 50°C and the bubble temperature was
kept constant at 7°C.
For this type of study, accurate thermodynamic refrigerant properties are

essential for pure refrigerants as well as for mixtures. To calculate these
properties is very time-consuming. Therefore, use was made of the NIST' 5
REFPROP database that can calculate the properties of 38 pure refrigerants on a
personal computer. It can also calculate the properties of mixtures of up to five
components from the list of 37 refrigerants, seeing that mixtures with ammonia
are not allowed. Although some of the refrigerants have already been phased out
by the Montreal Protocol, they were included in this study so that the results
could be compared to the refrigerants which over the years developed as the
"favourites" and benchmarks for certain applications.
6
1.4 SCOPE OF THIS STUDY
The outline of this paper is as follows: Part I deals with pure refrigerant
refrigeration cycles and Part II is devoted to non-azeotropic mixtures. In each
part the refrigerants considered are given, the cycle analyses are explained,
whereafter the results are discussed taking into consideration the environmental
impact.
CHAPTER TWO
8
2. PART I: PURE REFRIGERANTS

2.1 INTRODUCTION
Table 1 lists the 34 pure refrigerants that are considered in this paper. From the
list of 38 refrigerants provided in REFPROP, not all of the pure refrigerants are
defined for the 7°C to 50°C temperature range, which means that their critical
points lay within or very close to this region. Since points close to the critical
point prompt unreliable results, the performance of the following pure
refrigerants: R13; R14; R23; R744 was not analysed.
R11 Trichlorofluoromethane R12 Dichlorodifluoromethane

R13 Chlorotrifluoromethane R13B1 Bromotrifluoromethane
R14 Tetrafluoromethane R21 Dichlorofluoromethane
R22 Chlorodifluoromethane R23 Trifluoromethane
R32 Difluoromethane R113 1,1,2-trichloro-1,2,2-trifluoroethane
R114 1,2-dichloro-1,1,2,2-tetrafluoroethane R115 Chloropentafluoroethane
R123 1,1-dichloro-2,2,2-trifluoroethane R123a 1,2-dichloro-1,1,2-trifluoroethane
R124 1-chloro-1,2,2,2- tetrafluoroethane R125 Pentafluoroethane
R134 1,1,2,2-tetrafluoroethane R134a 1,1,1,2-tetrafluoroethane
R141b 1,1-dichloro-1-fluoroethane RC270 Cyclopropane
R142b 1-chloro-1,1-difluoroethane RC318 Octafluorocyclobutane
R143 1,1,2-trifluoroethane R227ea 1,1,1,2,3,3,3-heptafluoropropane
RI43a 1,1-difluoroethane R236ea 1,1,1,2,3,3-hexafluoropropane
R152a 1,1,2-trifluoroethane R245cb 1,1,1,2,2-pentafluoropropane
R218 Octafluoropropane R600 Butane
R290 Propane R600a 2-methylpropane
Pentane 2-methylbutane
R744 Carbon Dioxide E134 Bis(difluoromethyl)ether
E245 2-(difluoromethoxy)-1,1,1- R717 Ammonia
trifluoroethane
Table 1. List of pure refrigerants analysed for spatial air conditioning applications
2.2 CYCLE ANALYSIS
Seeing that this study focuses on wet compression, it inevitably implies that
many calculations will be done based on data from within the two- phase region.
It is as a result of this that the evaluation takes place over a wide spectrum of
compressor inlet vapour qualities. This quality ranges from 0.3 to 1.0 in
increments of 0.1, and for superheat values of 10°C and 20°C. Some refrigerants
were evaluated from a higher quality, for example R134a. This is due to the fact
that in some cases isenthalpic expansion through the expansion valve leaves the
9
refrigerant at a higher vapour quality than 0.3 at the evaporator inlet, which
results in, when attempting calculation, ambiguous refrigerant performance
values.
The specific work done by the compressor, specific cooling capacity, COP C ,
refrigerant circulated for one kilowatt of cooling and compressor displacement
per kilowatt of cooling, were calculated for each of the refrigerants in Table 1
for the different compressor inlet qualities discussed in the previous paragraph.
A compressor isentropic efficiency of 75% was used and the condenser sub-
cooling was assumed to be zero. Isenthalpic expansion was also used for all
refrigerants and zero pressure drop was assumed through the condenser and
evaporator.
The performance of the different refrigerants for air conditioning applications

were calculated as follows (referring to Figure 2):
The specific work done by the compressor for dry or superheated compression is
calculated as
w= h2 -hl (1)
The specific work done by the compressor for wet compression is calculated as
w = hr- hi. (2)
The value of hl' is calculated on the evaporating pressure line as
hi .(x)= hr + x(hg - h r) (3)
The specific cooling capacity for dry compression is calculated as
q= - ha
while the specific cooling capacity for wet compression is calculated as
q=hr -h4
The cooling coefficient of performance for dry compression is
COP = (hi - ha)/(h2 -

10
The cooling coefficient of performance for wet compression is calculated as
COP = (h• -114)/(hr- hi•) (7)
The required refrigerant mass flow for 1 kW of cooling for dry compression is
calculated as
mr = 1/(h i - ha ) (8) •
The required refrigerant mass flow for 1 kW of cooling for wet compression is
calculated as
mr = 1/(hi• - ha ) (9)
The required compressor displacement rate per kilowatt of cooling for dry
compression is calculated as
V= (1/(h i - h4 ))p *1000 (10)
The required compressor displacement rate per kilowatt of cooling for wet
compression is calculated as
V= (1/(h• - h4 ))p *1000 (11)
The compressor discharge temperature was also obtained from the condensing
pressure and enthalpy at point 2.
2.3 RESULTS
The values obtained from using this method, is a good reflection of a refrigerant
under the same conditions in practice. The method does however not take into
account the pressure losses incurred in the evaporator and condenser and the
input power needed for example for fans and auxiliary equipment. This fact
must be kept in mind when reviewing this work, since the results produced will
lead for example to higher COP c's than would be experienced in practice.
Furthermore, the methodology followed resulted in a large volume of data of
which the detailed results are reproduced in the Appendices. The results are
represented in Appendices AAAA to AABL. Only limited results will be presented
in this document due to the fact that the results were specifically selected to
present a sufficient understanding and perspective of the use of wet compression
versus dry compression.
11
2.3.1 PERFORMANCE
The results for air conditioning, using three different refrigerants, are shown in -
Figures 3 to 6. The .three different refrigerants used in this comparison, E245,

R143 and NH3, were chosen for they represent the three typical kinds of trends
identified in the analyses. Reviewing the COPS results in Figure 3, it can be seen
that wet compression is advantageous for NH3, and not so advantageous for
E245. For R143 a marginal success is achieved with the use of wet compression.
NH3
R143
E245
00 C.' U
0 0 0 0 0 0
csi
Vapour quality
Figure 3 The COPS results for cooling R143, E245 and NH3
The cooling capacity results (Figure 4) shows that for NH3 and to .a lesser extent
with R143, the rate in increase of cooling capacity decreases as the vapour
quality approaches one. With E245, the rate in increase of cooling capacity
remains constant. Generally the cooling capacity decreases with wet
compression as can be expected, although the gradient changes at an inlet
vapour quality of one.
1200
1000 —
71) 800 NH3
600 -`- R143
cr 400 — E245
........
200 — ......... -
....... -
0 ... ".
I I I I
M Tr v-) `0 N 013.
6 6 6 0 o 0
O
•—• Cs1
Vapour quality
Figure 4 The specific cooling capacity results R143, E245 and NH3
12
250.00
200.00
150.00
NH3
an
sal 100.00 R143
50.00 - E245
0.00
0
0 0 0 0 0 • 0
0 0
N •
Vapour quality
Figure 5 The amount of refrigerant circulated for each kilowatt of cooling using R143, E245 and
NH3
Reviewing the results for refrigerants circulated (Figure 5) and compressor

displacement (Figure 6), it can be concluded that in both cases for NH 3 , the
refrigerant circulated or compressor displacement stays relatively constant with
changes in vapour quality. However, when E245 or R143 is used, both the
refrigerant circulated and compressor displacement show a substantial increase
with wet compression. It should be noted that the compressor displacement
needed for NH 3 for one kilowatt of cooling is much lower than for the other
refrigerants. A physically smaller compressor can therefor be used, which is
very advantageous.
60.00
50.00
40.00 -
NH3
1-1 30.00
. 8143
20.00 E245
10.00
0.00
v. Is al O I I
0 0 o 0 0 0 0 W
0 0
Vapour quality
Figure 6 The compressor displacement rate for each kilowatt of cooling using R143, E245 and
NH3
13
2.3.2 SUMMARY OF RESULTS
Table 2 lists the highest COP values obtained through calculation for every pure
refrigerant considered, whether it is with wet or dry compression. Also tabulated
are the corresponding specific cooling capacity (kJ/kg) and compressor
displacement (1/s)/(kW cooling) values. These values are compared with the
values obtained at 10°C superheat, since it is commonly found in practise that
the refrigerant is compressed at this superheated value.
From Table 2 it can be seen that the following refrigerants respond favourably
to wet compression as they have higher COP c values in the two-phase region:
R32 and NH3.
Table 3 gives the percentage improvement due to wet compression. The

percentage improvement is calculated by using the maximum value for wet
compression and comparing it with the value achieved when the refrigerant is
superheated by 10°C.
The highest COP value, that of ammonia, is obtained through the process of wet
compression. A COP value of 4.28 at a vapour quality of 0.9 is 7.2% higher than
the COP value of 3.99 at 10°C. Ammonia's specific cooling capacity decreased
with 14.3% against the 16.8% decrease considering R32. Wet compression of
ammonia doesn't affect the required compressor displacement rate to acquire
lkW of cooling.
It should be noted that although the COP values increase substantially, the
specific cooling capacity decreases. In the case of R32 the required compressor
displacement rate to acquire 1 kW of cooling increases with 3.1%. This means
that for wet compression more of the refrigerant is needed to have the same
cooling affect obtained from dry compression, which may require larger and
more expensive compressors.
14
Pure Refrigerant Vapour Quality COP Value Specific Cooling Compressor

capacity displacement
[kJ/kg] [(l/s)/kW Cooling]
R11 0.9
1.0
10°C SH 4.281 152.4 2.083
20°C SH
R12 0.9
1.0
10°C SH 3.88 110.7 0.428
20°C SH
R13b1 0.9
1.0
10°C SH 3.221 58.4 0.224
20°C SH 3.328 63.9 0.217 .
R21 0.9 ,
1.0 4.262 195.5 1.192
10°C SH 4.255 201.4 1.202
20°C SH
R22 0.9
1.0 3.828 147.0 0.259
10°C SH 3.802 1.54.1 0.261
20°C SH
R32 0.9 3.775 206.56 0.167
1.0
10°C SH 3.65 248.2 0.162
20°C SH
R113 0.9
1.0
10°C SH 4.191 123.5 4.893
20°C SH 4.289 129.8 4.821
R114 0.9 •
1.0
10°C SH 4.009 98.9 1.213
20°C SH
R115 0.9
1.0
10°C SH 3.291 64.5 0.380
20°C SH 3.484 72.0 0.359
R123 0.9
1.0
10°C SH 4.190 141.9 2.45
20°C SH 4.222 148.6 1.425
R123a 0.9
1.0
10°C SH 4.195 143.2 2.645
20°C SH 4.245 150.0 2.616
Table 2 A summary of the maximum COPc values obtained through calculation for every pure
refrigerant. Also tabulated are the corresponding specific cooling capacity (kElcg) and
compressor displacement (Us)/(kW cooling) values. These values are compared with the values
obtained at 10°C superheat, since it is commonly found in practise that the refrigerant is
compressed at this superheated value
15

(kJ/kg] [(1/s)/kW Cooling]
R124 0.9
1.0
10°C SH 3.909 115.7 0.683
20°C SH 3.980 123.1 0.669
R125 0.9
1.0
10°C SH 3.148 76.4 0.266
20°C SH 3.260 85.2 0.253 •
R134 0.9
1.0 •
10°C SH 3.962 155.3 0.493
20°C SH 3.988 164.3 0.486 .
R134a 0.9
1.0
10°C SH 3.825 143.3 0.405
20°C SH 3.891 152.0 0.399
R141b 0.9
1.0 4.329 184.7 2.762
10°C SH 4.294 191.8 2.760
20°C SH
R142b 0.9
1.0
10°C SH 4.102 167.9 0.726
20°C SH 1.121 176.4 0.719
R143 0.9
1.0
10°C SH 4.157 246.1 0.983
20°C SH 4.163 255.3 0.983
R143a 0.9
1.0
10°C SH 3.43 125.3 0.257
20°C SH 3.516 135.5 0.251
R152a 0.9
1.0 -
10°C SH 4.011 239.6 0.421
20°C SH 4.028 250.3 0.420
R218 0.9
1.0
10°C SH 2.86 45.0 0.469
20°C SH 3.105 53.4 0.418
R290 0.9
1.0
10°C SH 3.713 262.9 0.314
20°C SH 3.77 281.0 0.309
RC270 0.9
1.0
10°C SH 4.04 345.3 359.3
20°C SH
Table 2 (continued)
16

[kJ/kg] [(1/s)/kW Cooling]
RC318 0.9
1.0
10°C SH 3.569 70.9 0.949
20°C SH 3.741 78.8 0.890
R227ea 0.9
1.0
10°C SH 3.561 77.4 0.658
20°C SH 3.711 85.6 0.622
R236ea 0.9
1.0 .
"10°C SH 3.954 120.2 L214
20°C SH 4.036 128.6 1.179
R245cb 0.9
1.0
10°C SH 3.692 101.9 0.629
20°C SH 3.84 111.1 0.602
R600 0.9
1.0
10°C SH 4.066 289.5 1.026
20°C SH 4.136 306.6 • 1.006
R600a 0.9
1.0
10°C SH 3.971 258.4 0.756
20°C SH 4.042 275.4 0.739
n-05 0.9
1.0
10°C SH 4.15 295.5 3.331
20°C SH . 4.24 312.1 3.268
i-05 0.9
1.0
10°C SH 4.123 275.4 2.557
20°C SH 4.201 291.8 2.503
E134 0.9
1.0
10°C SH 4.03 168.2 1.126
20°C SH 4.101 176.6 1.113
E245 0.9
1.0
10°C SH 4.073 145.0 2.679
20°C SH 4.182 153.9 2.616
NH3 0.9 4.278 904.17 0.226
1.0
10°C SH 3.99 1054.9 0.226
20°C SH
Table 2 A summary of the highest COP values obtained through calculation for every pure
refrigerant. Also tabulated are the corresponding specific cooling capacity (k.1/kg) and
compressor displacement (1/s)/(kW cooling) values. These values are compared with the values
obtained at 10°C superheat, since it is commonly found in practise that the refrigerant is
compressed at this superheated value
18
—_
101°C
Temperature [°C] •
50° Conden m
7°C Evaporat
-49°C
Entropy [kJ/kg•K]
Figure 8 The T-s graph of RC318 as an example of a curve with a re- entrant saturated
vapour line
Refrigerants with a bell- shaped Refrigerants with a re- entrant saturated

T-s curve vapour line T-s curve
R11 R13
E134 n-05
RI 2 R600a
R125 E2 4 5
R134 R123
R134a R123a
R13B1 R124
R14 R113
R142b R218
R143 RC318
R143a R227ea
R152a R236ea
R21 R114
R22 R600
R23 R115
R290 i-05
R32 R245cb
R717 (NI-13) R141b
R744
RC270 .
Table 4 The considered pure refrigerants are divided into two groups: Those refrigerants with a
bell- shaped T-s curve (refer to Figure 7); and those refrigerants with a T-s curve with a re-
entrant saturated vapour line (refer to Figure 8).
19
None of the refrigerants with re-entrant saturated vapour lines prompted results
with higher COP values when considering wet compression. On the other hand,
not all the refrigerants with bell-shaped T-s curves proved advantageous to the
practise of wet compression. The refrigerants mentioned above for which wet
compression is advantageous, all fall in the bell-shaped T-s graph group, and yet
not all the refrigerants enjoy the advantages of wet compression.
2.3.4 CONCLUSION
From the 34 pure refrigerants analysed, all those with re-entrant saturated
vapour lines produce better COP c 's when the refrigerant is superheated before
entering the compressor. Only two of the refrigerants (R32 and NH3) with bell-
shaped T-s curves, consistently produce higher COI:Vs when wet compression is
used. It can therefore be concluded that in general it has been found that wet
compression is not attractive when pure refrigerants are used.
20
CHAPTER THREE
21
3. PART H: BINARY NON-AZEOTROPIC REFRIGERANT MIXTURES
3.1 INTRODUCTION
The analysis of a non-azeotropic yields different results to that of a pure

refrigerant. This is due to the fact that a mixture of two refrigerants can produce
many different refrigerants by just changing the mass ratio. In this study, the
mass ratio was changed over the entire spectrum of the different components of
a mixture, but at intervals of 10% at a time. A total of 31 binary refrigerant
mixtures were analysed in this way, resulting in 279 different mixtures being
analysed. Table 5 lists the refrigerant mixtures analysed.
Refrigerant Mixtures
R11/R114 R143/R43a R32/R143
R12/R152a R22/R114 R32/R152a
R12/R22 R22/R134a R13b1/R152a
R123/R134a R22/R142b R32/R142b
R124/R125 R22/R152a R22/R124
R125/R142b R22/R218 R22/R143
R125/R143 R290/R600 R218/RC318
R125/R143a R32/R124 R134a/R143
R125/RC318 R32/R125 R12/R13
R134a/R143a R32/R134a R124/R143a
R142b/R143a
Table 5 A list of the refrigerant mixtures-analysed.
The refrigerant mixtures selected were refrigerants that had recently been
considered in literature (References 2 to 11, 16 and 17). In literature, either
specific or just a few mixing concentrations were considered, where the full
range of concentrations was considered in this study.
As with pure refrigerants, some mixtures at certain mass ratios were omitted
from the analyses because their critical temperatures would come to close to the
dew point temperature of 50°C for air conditioning applications.
3.2 CYCLE ANALYSES
The process of analysing a non-azeotropic mixture remains in principle the same

as that of a pure refrigerant. There is, however, one major difference in the way
the inputs to the analyses are defined. This is due to the fact that the
evaporation and condensation processes do not occur at constant temperatures as
with pure refrigerants. Figure 9 gives an explanation of the definition of the
inputs to the analyses . In this study, the evaporation temperature at the inlet of
.
22
the evaporator (point A), the bubble point, corresponds to the evaporation
temperature use with the pure refrigerant. The inlet of the condenser (point B),
the dew point, is at the same temperature as that for the condensation process of
the pure refrigerant.
The quality ranges investigated were again from 0.3 to one in increments of 0.1
as well for superheat values of 10°C and 20°C. The compressor isentropic
efficiency, sub-cooling, expansion and pressure drop assumptions, were the
same as for pure refrigerants.
Tcond Yil•••••••••■■■••••
Pure refrigerant
Non-azeotrone
Tevap
Figure 9 A comparison between the evaporation and condensation temperatures of a pure

refrigerant, and the bubble point and dew point temperatures of a non-azeotropic mixture
3.3 RESULTS
During the analyses of the various refrigerant mixtures, an enormous amount of

results were produced in the shape of graphs and tables. These results are
reproduced in detail in the Appendices. The results for air conditioning are
reproduced in Appendix ABAAA through Appendix ABBEI. For the purpose of the
discussion, only some results were chosen to present a sufficient understanding
and perspective of the use of wet compression. For this reason, the results of
each mixture considered are summarised in Table 6. It identifies the maximum
COP c for wet and dry compression. Note that Table 6 has an addition not found
in Table 2, namely the number found in the first column under each of the
refrigerant mixtures. This number indicates the evaporation temperature glide
for that particular mixture.
23
Non-azeotropic Performance Vapour Quality

mixture characteristics
0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R11/R114 COP 4.360 4.141
(0.1/0.9) Specific cooling capacity 99.4 106.0
1.14 Compressor displacement 1.266 1.236
R11/R114 COP 4.551 4.294
R11/R114 COP 4.605 4.5
R11/R114 COP 4.935 4.566
.
R11/R114 COP 4.642 4.688
R11/R114 COP 4.700
(0.6/0.4) Specific cooling capacity 136.6
3.42 Compressor displacement 1.502
R11/R114 COP 4.641 4.697
R11/R114 COP 4.688 4.610
R11/R114 COP 4.552 4.454
R12/R152a COP 4.154 4.138
(0.1/0.9) Specific cooling capacity 213.8 224
R12/R152a COP 4.197 4.258
R12/R152a COP 5.134 5.121
R12/R152a COP 4.103 4.099
1.75 . Compressor displacement 0.359 0.357
R12/R152a COP 4.452 3.989
• 1.07 Compressor displacement 0.378 0.342
R12/R152a COP 4.326 4.004
R12/R152a COP - 3.868 3.894
Table 6 (continued) A summary of the maximum COP and corresponding specific cooling
capacity (kJ/kg) and compressor displacement (Us) per kilowatt of cooling. Also tabulated are the
same values obtained at 10°C superheat
24

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R12/R152a COP 3.940 3.953
R12/R152a COP 3.974 4.004
R12/R22 COP 3.809
R12/R22 COP 4.154 3.809
R12/R22 COP 4.116 3.806
R12/R22 COP 4.17 3.876
R12/R22 COP 4.003 3.982
R12/R22 COP 4.135 4.084
R12/R22 COP 4.355 4.233
R12/R22 COP 4.321
R12/R22 COP 4.237 4.204
R123/R134a COP 4.663 4.677
R123/R134a COP 5.901 5.922
R123/R134a COP 7.629 7.640
- 17.71 Compressor displacement 0.385 0.383
R123/R134a COP 9.604 9.700
Table 6 (continued) A summary of the highest COP and corresponding specific cooling capacity
(kJ/kg) and compressor displacement (I/s)/(kW cooling) values obtained through calculation for
each refrigerant mixture. Also tabulated are the same values obtained at 10°C superheat
25

mixture characteristics .
0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R123/R134a COP 11.73 11.84
R123/R134a COP 14.07
R123/R134a COP - 14.75 14.58
R123/R134a COP 13.24
R123/R134a COP 9.11 9.168
R124/R125 COP ..:''''; 3.827 3.952
R124/R125 COP 4.438 4.576
R124/R125 COP 5.002 5.110
R124/R125a COP 5.478 5.593
R124/R125 COP 5.859 5.913
R124/R125 COP 5.895 6.051
R124/R125 COP 5.826 5.779
R124/R125 COP 5.376 5.431
(0.8/0.2) .Specific cooling capacity 124.0 131.8
R124/R125 COP 4.686 4.782
R124/R143a COP 3.738 3.835
(kJ/kg) and compressor displacement (1/s)/(kW cooling) values obtained through calculation for
26

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH- SH
R124/R143a COP 4.116 4.161
4.61 ..
Compressor displacement 0.255 0.25
R124/R143a COP 4.477 4.591
(0.3/0.7) Specific cooling capacity - 136.1 145.7
6.80 ' Compressor displacement 0.257 0.252
R124/R143a COP 4.903 5.019
R124/R143a COP 5.341 5.358
10.14 Compressor displacement 0.271 0.267 .
R124/R143a COP 5.661 5.68
R124/R143a COP 5.791 5.821
(0.7/0.3) Speci fi c cooling capacity .::"-
138.2 146.7
R124/R143a COP 5.669 5.69
10.09' Compressor displacement 0.363 0.358
R124/R143a COP 5.254 4.978
R125/R142b COP 4.871 4.893
R125/R142b COP 5.623 5.638
R125/R142b COP 6.187 6.262
R125/R142b COP 6.586 6.587
R125/R142b COP 6.663 6.767
R125/R142b COP 6.490 6.608
R125/R142b COP 5.924 6.103
27

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R125/R142b COP 5.171 5.254
R125/R142b COP 4.192 4.32
R125/R143 COP 5.873 5.813
R125/R143 COP 7.488 7.532
15.78 Compressor displacement 0.451 0.451'
R125/R143 COP 9.111
R125/R143 COP .- :10.19 10.0
(0.4/0.6) Specific cooling capacity _. 217.4 226.7
R125/R143 COP 10.16 10.58
R125/R143 COP 10.16 10.58
R125/R143 COP 8.775 8.762
R125/R143 COP 6.895 7.095
R125/R143 COP 4.937 5.031
R125/R143a COP 3.403 3.517
R125/R143a . COP 3.390 3.492
R125/R143a COP 3.405 3.461
R125/R143a COP 3.367 3.466
R125/R143a COP 3.307 3.421
(kJ/kg) and compressor displacement (Us)/(kW cooling) values obtained through calculation for
28

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R125/R143a COP 3.321 3.377
R125/R143a COP 5.067 5.087
R125/R143a COP 3.211 3.285
R125/RC318 COP 7.278 7.457
R125/RC318 • COP 8.778 8.992
R125/RC318 . COP 8.667 8.984
R125/RC318 COP 7.56 7.597
R125/RC318 COP 6.168 6.40
R125/RC318 COP 4.987 5.202
R125/RC318 COP 4.196 4.376
R125/RC318 COP 3.589 3.737
R125/RC318 COP 3.282 3.389
R134a/R143a - COP 3.587 3.666
R134a/R143a COP 3.747 3.827
' 2.01 Compressor displacement 0.262 • 0.256
R134a/R143a COP . 3.866 3.938
R134a/R143a COP 3.990 4.081
29

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R134a/R143a COP 4.085 4.121
R134a/R143a COP 4.115 4.132
R134a/R143a COP 4.115 4.156
R134a/R143a COP 4.065 4.132
R134a/R143a COP 4.011 4.08
R142b/R143a COP 4.096 4.166
(0.1/0.9) Specific cooling capacity 140.9 _ 151.1
R142b/R143a COP 4.767 4.818
R142b/R143a COP 5.348 5.434
R142b/R143a COP 5.877 5.830
R142b/R143a COP 6.185 6.258
R142b/R143a COP 6.242 6.333
R142b/R143a COP 6.276 6.084
R142b/R143a COP 5.871 5.631
R142b/R143a COP 5.091
• 5.88 Compressor displacement 0.529
R143/R143a COP 4.618 4.664
R143/R143a COP 5.929 6.003
30

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R143/R143a COP 7.265 7.211
R143/R143a COP 8.295 8.343
R143/R143a COP 7.354 7.333
R143/R143a COP 9.123 5.557 -
20.66 Compressor displacement 0.302 0.317 •
R143/R143a COP 8.613 8.480
R143/R143a COP 7.343 7.398
R143/R143a COP 6.588 5.917
R22/R114 COP 7.430 7.494
R22/R114 COP 9.189 9.256
R22/R114 COP 9.224 9.136
R22/R114 COP 8.361 8.454
R22/R114 COP 7.160 7.184
R22/R114 COP 9.197 9.036
R22/R114 COP 5.229 5.283
9.66 Compressor diiplacement 0.268 0.268
R22/R114 COP 4.582
31

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R22/R114 COP 4.152 4.12
R22/R134a COP 3.954 3.999
R22/R134a COP 4.026
R22/R134a COP 4.042 4.061
R22/R134a COP 4.011 4.054
R22/R134a COP - 4.03 4.042
R22/R134a COP 3.963 3.987
R22/R134a COP 4.890 3.954
1.15 Compressor displacement - 0.295 0.281
R22/R134a COP 4.487 3.907
R22/R134a COP - 4.286 3.851
R22/R142b COP . 5.201 5.000
R22/R142b COP 5.709 5.637
R22/R142b COP 6.023 6.056
R22/R142b COP 6.214 6.205
R22/R142b COP 6.072
32

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R22/R142b COP 5.880 5.761
R22/R142b COP 5.39 5.374
R22/R142b COP 4.898
R22/R142b COP 4.363 4.338
R22/R152a COP 4.041 4.042
R22/R152a COP 4.015 4.029
R22/R152a COP 4.103
R22/R152a COP 4.158 4.141
(0.4/0.6) Specific cooling capacity 207.9 217
R22/R152a COP 4.221
R22/R152a COP 4.299 4.283
R22/R152a COP 5.390 4.408 4.363
(0.7/0.3) Specific cooling capacity 84.8 186.9 194.9
2.87 Compressor displacement 0.331 0.311 0.312
R22/R152a COP 4.377
(0.8/0.2) Specific cooling capacity 185
R22/R152a COP 4.232
R22/R218 COP 3.326 3.578
R22/R218 COP 3.375 3.573
33

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R22/R218 COP 3.323 3.481
R22/R218 COP 3.303 3.456
R22/R218 COP 3.413 3.507
R22/R218 COP 3.611 3.6g1
0.79 Compressor displacement 0.254 0.249 '
R22/R218 COP 3.807 3.843
R22/R218 - COP 3.917 3.938
R22/R218 COP 4.246 3.926
R290/R600 COP 5.255 5.322
R290/R600 COP 6.125 6.209
R290/R600 COP 6.655 6.727
'13.38 Compressor displacement 0.448 0.443
R290/R600 COP 6.796 6.883
R290/R600 COP 9.375 9.461
(0.5/0.5) Specific cooling capacity. 335.0 353.2
R290/R600 COP 6.242 6.300
R290/R600 COP 5.678 5.704
11.06 Compressor displacement 0.320 0.316:
R290/R600 COP 5.023 5.067
(0.8/0.2) Specific cooling capacity _ 302.7 320.9
34

0.6 0.7 0.8 0,9 1.0 10°C 20°C
SH SH
R290/R600 COP 4.347 4.408
R32/R124 COP 9.023 9.204
R32/R124 COP 9.827 9.778
(0.2/0.8) Specific cooling capacity 166.4 '174.7
R32/R124 COP 8.370 8.300 .
19.85 Compressor displacement . 0.171 0.172
R32/R124 COP 6.704
R32/R124 COP 5.474 5.393
R32/R124 COP 4.613 4.591
R32/R124 COP 4.154 4.068
R32/R124 COP 3.880 3.805
R32/R124 COP 3.863 3.688
R32/R125 COP - 3.225 3.335
R32/R125 COP 3.338 3.366
R32/R125 COP 3.473 3.603
R32/R125 COP 3.411 3.421
R32/R125 - COP 3.43 3.462
35

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R32/R125 COP 3.518 3.488
R32/R125 COP 3.567 3.528
R32/R125 COP 3.629 3.583
R32/R134 COP 5.248 5.063 '
R32/R134 COP 5.630 5.595
R32/R134 - COP 5.696 5.662
R32/R134 COP 5.524 5.482
R32/R134 COP 5.191 5.152
R32/R134 COP 4.867 4.819
R32/R134 COP 4.565 4.479
R32/R134 COP 4.220 4.170
14.32/R134 COP 4.001 3.873
R32/R143 COP 7.834 7.769
R32/R143 COP 10.93 10.81
R32/R143 COP 13.0 12.63
36

0.6 0.7 0.8 0.9 1.0 10°C. 20°C
SH SH
R32/R143 COP 12.69 12.54
R32/R143 COP 11.43 11.34
R32/R143 COP 9.689 9.586
R32/R143 COP 7.816 7.663
19.70 Compressor displacement 0.161 0.163 "
R32/R143 COP 6.132 6.023
R32/R143 COP 4.807 4.678
(0.9/0.1) . Specific cooling capacity 228.4 270.7
R32/R152a COP 4.569 4.527
3.66 • Compressor displacement 0.336 0.337
R32/R152a COP 4.924 4.899
R32/R152a COP 5.100 5.091
R32/R152a COP 5.157 5.117
R32/R152a COP 5.110 5.031
R32/R152a COP ' 4.926 4.881
R32/R152a COP 4.66 4.614
R32/R152a COP 4.421 4.308
R32/R152a COP 4.021 3.988
(kJ/kg) and compressor displacement (l/s)/(kW cooling) values obtained through calculation for
37

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R13b1/R152a COP 4.816 4.773
R13b1/R152a COP 5.537 5.406
R13b1/R152a COP 5.882
11.74 Compressor displacement 0.249 .
R13b1/R152a COP 6.142
R13b1/R152a COP 5.893 5.912
R13b1/R152a COP 5.525
(0.6/0,4) Specific cooling capacity 138.5
R13b1/R152a COP 4.817 4.899
R13b1/R152a COP 4.114 4.138
R13b1/R152a COP 3.554
R32/R142b COP 7.056 6.927
R32/R142b COP 8.596 8.344
R32/R142b COP 8.751 8.656
R32/R142b COP 8.148 8.093
R32/R142b COP 7.312 7.182
. 16.69 Compressor displacement 0.180 0.182
R32/R142b COP 6.270 6.233
38

0.6 0.7 0.8 0.9 1.0 10°C 20°C
. SH SH
R32/R142b COP 5.417 5.369
R32/R142b COP 4.712 4.642
R32/R142b COP 4.125 4.054
1222/R124 COP 4.887 4.639 '
4.45 Compressor displacement 0.539 0.508 •
R22/R124 COP 5.019 5.047
6.70 Compressor displacement 0.42- 0.415
R22/R124 COP ,5.188 5.101
R22/11(124 COP 5.130 5.150
R22/R124 COP 4.970 5.016
R22/R124 COP 4.725 4.777
R22/R124 COP 4.551 4.512
R22/R124 COP 4.291
R22/R124 COP 4.041 4.032
R22/R143 COP 5.531 5.225
6.83 Compressor displacement _ 0.698 0.682
R22/R143 COP 6.344 6.181
R22/R143 COP 6.882 6.869
(kJ/kg) and compressor displacement (l/s)/(kW cooling) values obtained through calculation for
39

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R22/R143 COP 7.328 7.204
R22/R143 COP 7.373 7.295
R22/R143 COP 7.117 7.043
R22/R143 COP 6.548 6.438 .
R22/R143 COP 5.657
R22/R143 COP 4.759 4.734
R218/RC318 COP 3.481 4.295
R218/RC318 COP 3.811 4.739
R218/RC318 COP 4.092 4.893
R218/RC318 COP 4.348 4.984
R218/RC318 COP 4.689 5.013
R218/RC318 COP 4.720 4.767
R218/RC318 COP 4.193 4.500
(0.7/0.3) Speci fi c cooling capacity 64.3 72.6
R218/RC318 COP 3.769 4.032
R218/RC318 COP 3.394 596
(0.9/0.1) Specific cooling capacity 52.53. 60.9
40

0.6 0.7 0.8 0.9 1.0 10°C 20°C
SH SH
R134a/R143 COP 4.652 4.603
3.07 . Compressor displacement 0.845 0.820
R134a/R143 COP 4.940
R134a/R143 COP 4.717 4.735
R134a/R143 COP 5.341 5.356
R134a/R143 COP 5.382 5.335
R134a/R143 COP 5.242 5.313
R134a/R143 COP 5.087 5.091
R134a/R143 COP 4.771
R134a/R143 COP 4.335 4.356
R12/R13 COP 3.007 3.066
R12/R13 COP 8.051 7.839
R12/R13 COP 9.287 9.108
R12/R13 COP 9.452
R12/R13 COP 8.257 8.351
(0.8/0.2) Specific cooling capacity _ 125.5 132.5
19.34 Compressor displacement 0.175 0.175 -
R12/R13 COP 6.250
Table 6 A summary of the highest COP and corresponding specific cooling capacity (kJ/kg) and
compressor displacement (l/s)/(kW cooling) values obtained through calculation for each
refrigerant mixture. Also tabulated are the same values obtained at 10°C superheat
41
The identification of the maximum COP c values in Table 6 was, however, not as
simple as for pure refrigerants. It was found that certain mixtures have
discontinuities in performance results at certain vapour qualities. In Figure 10,
an example is given of R13b1 with R152a at a concentration of 10%/90%. It can
be concluded that an unexpected peak exists at a vapour quality of 0.6. The
reason for these peaks or dips, which occurred rather frequently, is unclear and
was not investigated in detail. It might be from inaccurate thermodynamic
properties predicted by REFPROP 15 or from inaccurate interaction parameters.
In REFPROP mixture calculations require interaction parameters for each binary
pair of components in the mixture. Values of interaction parameters based on
experimental data are stored within REFPROP for more than 60 binary pairs,
whereas other pairs are calculated using an estimation algorithm.
Reviewing Table 6, it seems from a COP c point of view that for air
conditioning, the following refrigerant mixtures respond consistently favourably
to wet compression: R11/R114, R12/R22, R124/R125, R142b/R143a,
,
R143/R143a, R22/R134a, R22/R142b, R22/R152a, R22/R218, R32/R124,

R32/R125, R32/R134, R32/R143, R32/R152a, R32/R42b, R22/R124,
R22/R143 and R134a/R124. The COP S 's vary between 3.3 at 20°C superheat for
R125/RC318 (0.9/0.1) to 14.75 at a vapour quality of 1.0 for R123/R134a
(0.7/0.3).
Calculated
Trend
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 IOSH 2OSH

Vapour quality
Figure 10 Graph showing the discontinuity in the calculation of the COP c values for
R13b1/R152a (0.9/0.1)
42
As with pure refrigerants, the specific cooling capacity decreases and the
compressor displacement increases with the use of wet compression as can be
expected. It was found, however, that for some refrigerant mixtures, for example
R32/R143 (0.3/0.7), the compressor displacement reaches a relative low value at
approximately the same vapour quality where the maximum COP, is reached
(see Figures 11, 12 and 13).. It is interesting to note that this phenomenon occurs
especially in refrigerant mixtures that produce higher COP values with wet
compression. The opposite also seems true: refrigerant mixtures for which the
compressor displacement decreases when it is superheated, do not tend to enjoy
the advantages of wet compression.
0.35 16
0.30 14
12
0.25
10
0.20 --4"-
- yr
8
j." 0.15 - —U—m
0.10 - - 4
-N
0.05 - 2
0.00 0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 10SH 20SH
Vapour quality
Figure 11 The compressor displacement and refrigerant circulated per
kilowatt of cooling for R32/R143 (0.3/0.7)
COP
Trend
1 2 3 4 5 6 7 8 9 10
Vapour quality
Figure 12 The COP. values for R32/R143 (0.3/0.7)
43
0.4 0.5 0.6 . 0.7 0.8 0.9 1 10SH 2OSH

Vapour quality
Figure 13 The specific cooling capacity and specific work for R32/R143 (0.3/0.7)
Table 7 is similar to Table 3 for pure refrigerants, but because of the amount of
refrigerant mixtures analysed, only the top 10 mixtures that gained the most in
COPE using wet compression, are presented. Reviewing Tables 3 and Table 7
together, it can be seen that the non-azeotropic mixtures tend to gain more from
wet compression than the pure refrigerants when considering the coefficient of
performance. The cooling capacities, however, decrease in general. Another
advantage of some of the non-azeotropes, is the fact that the compressor
displacement does not necessarily increase substantially when wet compression
is applied.
Non-azeotropic mixture Performance Vapour 10°C Percentage change

characteristics Quality-0.9 superheat %
R12/R152a COP 4.452 3.989 11.6
'(0.5/0.5) Specific cooling capacity 133.8 163.8 -18.3
Compressor displacement 0.378 0.342 10.5
R143/R143a COP 6.588 5.917 11.3
(0.9/0.1) Specific cooling capacity 215.9 255.6 -15.5
R12/R22 COP 4.154 3.809 9.1
- R12/R22 COP . 4.116 3.806 8.2
R22/R218 COP 4.246 3.926 8.2
(0.9/0.1) Specific cooling capacity . 114.9 140.8 -18.4
Table 7 The top 10 refrigerant mixtures with the highest percentage improvement in COP
obtained by using wet compression over dry compression. Also tabulated are the changes in
COP-, specific cooling capacity- and compressor displacement values relative to the values at
10°C superheated as a percentage
44
Non-azeotropic mixture Performance Vapour 10°C Percentage change

characteristics Quality-0.9 superheat %
R12/R22 COP 4.170 3.876 7.6
R22/R143 - COP 5.531 5.225 5.9
R22/R124 COP 4.887 4.639 5.3
R32/R124 COP 3.863 3.688 4.7
R142b/R143a COP 5.871 5.631 4.3
Table 7 (continued) The top 10 refrigerant mixtures with the highest percentage
improvement in COP obtained by using wet compression over dry compre§sion. Also tabulated
are the changes in COP-, specific cooling capacity- and compressor displacement values relative
to the values at 10°C superheated as a percentage
The highest percentage improvement in COP, 11.6%, is found through the

process of wet compression when considering R12/R152a (0.5/0.5) at a vapour
quality of 0.9. A COP value of 4.45 at a vapour quality of 0.9 is 11.6% higher
than the COP value of 3.99 at 10°C superheat, and 3.9% higher than the 4.28 of
Ammonia (best performing pure refrigerant) at the same vapour quality. The
specific cooling capacity decreased with 18.3%, while the required compressor
displacement rate to acquire lkW of cooling increased with 10.5%.
Although the COP value increased favourably, the changes in the specific
cooling capacity and the compressor displacement values really lower the newly
generated expectation and excitement that wet compression seems to have
working with this non-azeotrope.
The second highest percentage improvement in COP (Table 7), 11.3%, is found
through the process of wet compression when considering R143/R143a (0.9/0.1)
at a vapour quality of 0.9. A COP, value of 6.59 at a vapour quality of 0.9 is
11.3% higher than the COP, value of 5.92 at 10°C superheat, and 35.1% higher
than the 4.28 of Ammonia (best performing pure refrigerant) at the same vapour
quality. The specific cooling capacity decreased with 15.5%, while the required
compressor displacement rate to acquire 1 kW of cooling increased with only
2.3%. From a specific cooling capacity and compressor displacement point of
view, this refrigerant mixture clearly outperforms the rest of the refrigerant
mixtures in Table 7.
45
It is interesting to note that R22 appears six and R12 five times in Table 7. Of
this 11 times they appear together three times as mixtures (R12/R22). R12's
composition ranges from 20% to 40%. As the composition of R12 increases, so
does the COP, percentage improvement decrease from 9.1% to 7.6%. The
specific cooling capacity and the compressor displacement seem to remain
constant.
Because of the vast amount of refrigerant mixtures analysed, the study produced
an interesting by-product. Quite a few of the mixtures analysed are not
commonly used today. The study therefor provides a look into the behaviour of
some of these less known refrigerant mixtures. One of the interesting
discoveries made is the high COP, values achieved using certain refrigerant
mixtures.
To obtain a holistic view of what all the results generated actually mean, it was
necessary to further investigate the results listed in the appendices as well as in .
Table 6. Up to this point most of the focus was on how the refrigerant mixtures
reacted to the process of wet compression. The question that now needs to be
answered is how the process of wet compression compares to that of dry
compression. It was decided to have a look at the highest performing refrigerant
mixtures from a COP, point of view.
Table 8 lists the top 30 refrigerant mixtures with the highest COP, values,
whether it is obtained by wet or dry compression. This means that Table 8,
which is solely based on the refrigerant mixture's ability to perform, represents
10.8% of the total refrigerant mixtures considered in this study. The refrigerants
are listed in an order of a decreasing COP, value. Apart from the COP, value,
the corresponding specific cooling capacity- and compressor displacement
values are also listed against the relevant vapour quality.
The highest COP, value of 14.75 was calculated for R123/R134a (0.7/0.3) at a vapour
quality of 1.0. The mixture has the highest temperature glide of all the mixtures
considered in Table 8, namely that of 27.29°C. It can be concluded that the high
COP, can be contributed to the low amount of work that needs to be done by the
compressor, seeing that the dew point is set at 50°C.
Table 8 is dominated by five R32/R143 entries. R123/R134a, R22/R114 and

R125/R143 each have four entries in Table 8. These four non-azeotropes (17
refrigerant mixtures) represent only 6.1% of the total 279 'refrigerant mixtures
analysed. It is further interesting to note that the same non-azeotropes represent
57% of the top 30 entries in Table 8.
46
Non-azeotropic Performance Unit of Vapour Quality

mixture characteristics measure
0.8 0.9 1.0 10°C 20°C
SH SH
R123/R134a COP [] , 14.75
(0.7/0.3) Specific cooling capacity [J1cg- ] 182.9
27.29 Compressor displacement [nrs s-1] 0.499 •
R123/R134a COP [] , 14.07
(0.6/0.4) Specific cooling capacity [J kg- 1 191.4
26.98 Compressor displacement [m3 s-1] 0.44
R123/R134a COP [] 13.24
(0.8/0.2) Specific cooling capacity [J kg-1 ] 185.3 .
R32/R143 COP [] , 13.0
(0.3/0.7) Specific cooling capacity [J kg 1 ] 238.1
R32/R143 COP [] , 12.69
R123/R134a COP ' [ ]- 11.84
(0.5/0.5) Specific cooling capacity [J kg' ] 197.3
R32/R143 COP [] 11.43
(0.5/0.5) Specific cooling capacity [J kg-1 ] 306.4
R32/R143 COP [] 10.93
(0.2/0.8) Specific cooling capacity [J kg-i ] 229.6
R125/R143 COP [] , 10.58
R125/R143 COP [] 10.19
(0.4/0.6) Specific cooling capacity [J 1] 217.4
22.23 Compressor displacement [m' s-1] 0.302
R32/R124 COP [] , 9.827
(0.2/0.8) Specific cooling capacity [J .1ce] 166.4
R123/R134a COP [] , 9.700
(0.4/0.6) Specific cooling capacity [J !ce.] 192.7
21.91 Compressor displacement' [m3 s-1] 0.390
R32/R143 COP [] 9.689
R290/R600 COP [] 9.461
(0.5/0.5) Specific cooling capacity [J kg-' ] 353.2
14.07 Compressor displacement [mi s-1] 0.354
R12/R13 COP [] 9.452
Table 8 The top 30 refrigerant mixtures with the highest COP, values, whether it is obtained
by using wet or dry compression. Also tabulated are specific cooling capacity- and compressor
displacement values at the relevant vapour quality
47
Non-azeotropic Performance Unit of Vapour Quality

mixture characteristics measure
0.8 0.9 1.0 10°C 20°C
SH SH
R12/R13 COP [] , 9.287
(0.6/0.4) Specific cooling capacity [J kg] 110.2 •
R22/R114 COP [ ]- 9.256
(0.2/0.8) Specific cooling capacity [J kg i ] 148.1
R22/R114 COP [] , 9.224
(0.3/0.7) Specific cooling capacity [J kg" ' ] . 140.2
R32/R124 COP [] , 9.204'
(0.1/0.9) Specific cooling capacity [J kg"'] 166.9
R22/R114 COP [] , 9.197
(0.6/0.4) Specific cooling capacity [J kg] 144.7
R123/R134a COP [ ]- 9.168
(0.9/0.1) Specific cooling capacity Pr Ici3 i l 179.7
18.86 Compressor displacement [n.? s-1] 0.905
R143/R143a COP [] 9.123
(0.6/0.4) Specific cooling capacity -I
[J kg ] 237.2
R125/R143 COP [] 9.111
(0.3/0.7) Specific cooling capacity [J kg '] 238.1
R125/RC318 COP [] 8.992
R125/RC318 COP [] 8.984
Ft125/R143 COP [] 8.775
(0.7/0.3) Specific cooling capacity [J kg-I ] 163.8
R32/R142b COP [] 8.751
R143/R143a COP []- 8.613
R32/R142b COP [] 8.596
(0.2/0.8) Specific cooling capacity [J kg- ]
' 163.9
18.25 Compress& displacement [m3 s-1] 0.27
R22/R114 COP [ ]- 8.454
Table 8 (continued) The top 30 refrigerant mixtures with the highest COP c values, whether
it is obtained by using wet or dry compression. Also tabulated are specific cooling capacity- and
compressor displacement values at the relevant vapour quality
48
Only 10% (3 out of 30) of the highest COP, values listed in Table 8 represent
refrigerant mixtures that respond positively to the process of wet compression.
Thus 90% of all maximum COP, values are achieved for superheating and not
with wet compression.
It is interesting to note that the first seven entries (23%) in Table 8 all have
temperature glides greater than 25°C. Eleven refrigerant mixtures (37%) have
temperature glides that lie between 20°C and 25°C. A further ten refrigerant
mixtures (33%) have temperature glides that lie between 15°C and 20°C. Only
two refrigerant mixtures (7%) have temperature glides that lie between 10°C and
15°C. None of the refrigerant mixtures that prompt the highest COP, (refer to
Table 8) values have temperature glides that lie between 0°C and 10°C.
it is interesting to note that it seems that the following trend exists: The higher
the temperature glide, the higher the COP,. It may be premature to make such a
statement based only on the data listed in Table 8 which represents only 11.8%
of the total refrigerant mixtures considered. Temperature glide is further
investigated in paragraph 3.3.1.
3.3.1 TEMPERATURE GLIDE
Considering the previous paragraph it is obvious that the temperature glide of

each refrigerant mixture plays an important role in how it will perform. Two
issues are investigated. The possibility to define an accurate approximation of
the COP, as a function of the temperature glide is investigated for all the
refrigerant mixtures in Table 6. The second issue is that of grouping the
refrigerant mixtures into three different temperature glide categories in order to
make relevant conclusions.
It seems that, from Table 8, the higher the temperature glide, the higher the
COP,. This seems obvious if one is reminded that the evaporator outlet
temperature is then closer to the condenser inlet temperature on the
Temperature-Entropy diagram. This results in less work required from the
compressor.
To prove the theory in the preceding paragraph, all the refrigerant mixtures
considered in this study needs to be taken into account. Table 6 lists the COP,
values, amongst others, obtained at various vapour qualities and superheat
values. To come to-any relevant conclusions on how the COP, and temperature
glide react to each other, any generalisation needs to be based on fact.
49
Considering Table6, the only common COP S value entered for all the refrigerant
mixtures is at 10°C superheat. Thus the only given constant is a compressor
inlet temperature of 10°C superheat, which also forms the base on which any
conclusions are made.
All the COP S values in Table 6 are sorted in a descending order, after which it is
plotted on a graph (refer to Figure 14) as a function of the corresponding
temperature glide.
COP versus Temperature glide

18
16 -
14 -
12 -
a. 10 -
0
0 8
6
4
2 COP, = 0.0005(T9)3 - 0.0093(T9)2 + 0.2302(T9)+ 3.5708
0
0 5 10 15 20 25 30
Tg
Figure 14 The COPS plotted as a function of the corresponding temperature glide

for all the non-azeotropes considered
A further objective is to formulate an equation to enable . designers of air

conditioners to make quick yet accurate judgements of what the COP S of any
given binary refrigerant mixture, undergoing the same refrigeration cycle, will
be. A trendline is added of which the equation is calculated.
COP, = 0.0005(T g ) 3 - 0.0093(T g ) 2 + 0.2302(T g )+ 3.5708 (12)
To use equation (12) to one's advantage, a binary mixture must be chosen to

begin with. Use a refrigerant database like REFPROP to calculate the relevant
temperature glide and use equation (12) to estimate what the COP C will be for
such a cycle. The calculation of the temperature glide consists only of a few
steps in REFPROP, which reduces the lead-time for an answer considerably.
50
Reviewing Figure 14 it can be seen that 82% of the refrigerants have COP c
values between 3 and 7. For the same refrigerants the temperature glide lie
between 0°C and 13°C. This means that 82% of all the refrigerants are
concentrated on only 10% of the total area represented by the graph.
The data in Figure 14 is plotted with a standard deviation of 10%. The trendline
is plotted from which Equation (12) is derived. It successfully predicts the COP,
.
as a function of the temperature glide and has an average error of 7%. 52% of
the calculated values of the COP, -by using Equation (12)- has a COP, error •
smaller than 5%. 31% of the refrigerant mixtures have errors between 6% and
10%. Twenty-five refrigerant mixtures (10%) have errors between 11% and 15%.
The remaining 7% refrigerant mixtures have errors higher than 15%.
The second issue is that of grouping the refrigerant mixtures into three different
temperature glide categories in order to make relevant conclusions. The majority
of the refrigerants fall into a category similar to the one in Figure 15. This is
the temperature glide for R13b1/R152a, and reviewing this, it can be seen that
for small quantities (10-20%) of a specific refrigerant in the mixture, it almost
behaves like an azeotrope and the glide is small. For mixtures where the mixing
ratio is in the region of 40%:60% to 50%:50%, the temperature glide reaches a
maximum.
Figure 15 The temperature glide distribution for R13b1/R152a
Another category of temperature glide distribution is like R32/R142b, which is

given in Figure 16. The glide reaches a maximum of around 19°C for low mass
ratios of R32. This type of distribution was also found in R32/R124, R12/R152a,
R123/R134a, R22/R114, R22/R152a and R12/R22.
51
Figure 16 The temperature glide distribution for R32/R142b
The third category is for the temperature glide distribution like R22/R218 as
shown in Figure 17. This distribution has a bathtub shape with the minimum
glide where the mass ratio of the binary mixture is 40%:60%. It therefor
becomes a near-azeotrope.
Figure 17 The temperature glide distribution for R22/R218
The refrigerant mixtures analysed were divided into three groups, according to
the amount of temperature glide during the evaporation process. Table 9
represents the top 30 refrigerant mixtures, based on maximum COP c , for a low
temperature glide (0-5°C), a medium temperature glide (5-10°C) and a high
temperature glide (>10°C).
52

(0°C-5°C) (5°C-I0°C) (>10°C)
R218/RC318 5.96(20SH) R143/R143a 6.588(0.9) R123/R134a 14.07(10SH)
(0.9/0.1) 60.9 (0.9/0.1) 215.9 • (0.6/0.4) 191.4
2.78 0.398 9.94 0.611 26.98 0.44
R12/R152a 5.121(20SH) • R22/R142b 6.056(20SH) R123/R134a 13.24(10SH)
(0.3/0.7) 249.2 (0.3/0.7) 195.4 (0.8/0.2) 185.3
2.18 0.296 9.97 0.368 25.26 0.614
R125/R143a 5.087(20SH) R22/R142b 5.880(0.9) R32/R143 13.0(0.8)
(0.8/0.2) 103.1 (0.6/0.4) 153.4 (0.3/0.7) 238.1
0.08 . 0.238 9,01 0.291 25.85 0.235
RI 1/R114 4.935(1.0) R125/R143 5.873(1.0) R32/R143 12.69(1.0)
(0.4/0.6) 119.1 (0.1/0.9) 239.6 (0.4/0.6) 308.0.
3.29 1.378 9.64 0.615 26.42 0.198
R22/R134a 4.890(0.9) R142b/R143a 5.871(0.9) R123/R134a 11.84(20SH)
(0.7/0.3) 123.8 (0.8/0.2) 149.7 (0.5/0.5) 197.3
1.15 0.295 9.54 0.438 25.05 0.407
R22/R124 4.887(0.9) R22/R142b 5.709(0.7) R32/R143 11.43(1.0)
(0.1/0.9) 103.1 (0.2/0.8) 109.7 (0.5/0.5) 306.4
4.45 0.539. 8.39 0.482 25.42 0.179
R134a/R143 4.735(20SH) R125/R142b 5.638(20SH) R32/R143 10.93(0.8)
(0.3/0.7) 237.4 (0.2/0.8) 177.4 (0.2/0.8) 229.6
4.26 0.690 9.03 0.443 22.94 0.297
R32/R142b 4.712(0.9) R32/R134 5.630(1.0) R125/R143 10.58(20SH)
(0.8/0.2) 209.0 (0.2/0.8) 185.4 (0.5/0.5) 221.4
6.90 0.169 9.75 0.255 23.31 0.264
R11/R114 4.700(10SH) R13b1/R152a 5.537(0.9) R125/R143 10.58(20SH)
(0.6/0.4) 136.6 (0.2/0.8) 179.4 (0.6/0.4) 22-1.4
3.42 1.502 9.20 0.292 23.01 0.264
R11/R114 4.697(20SH) R22/R143 5.531(0.9) R125/R143 10.19(1.0)
(0.7/0.3) 147.8 (0.1/0.9) 212.3 (0.4/0.6) 217.4
3.14 1.588 6.83 0.698 22.23 0.302
R11/R114 4.688(20SH) R124/R125 5.431(20SH) R32/R124 9.827(1.0)
(0.5/0.5) 137.5 (0.8/0.2) 131.8 (0.2/0.8) 166.4
3.51 1.409 8.59 0.399 21.07 0.187
R11/R114 4.688(0.9) R22/R142b 5.39(0.6) R123/R134a 9.700(20SH)
(0.8/0.2) 122.8 (0.7/0.3) 84.80 (0.4/0.6) 192.7
2.50 1.774 7.29 0.331 21.91 0.390
R134a/R143 4.652(0.9) R134a/R143 5.382(1.0) R32/R143 9.689(1.0)
(0.1/0.9) 203.5 (0.5/0.5) 203.8 (0.6/0.4) 301.0
3.07 0.845 8.35 0.512 23.2 0.167
R11/R114 4.605(0.9) R134a/R143 5.356(20SH) R290/R600 9.461(20SH)
(0.3/0.7) 97.69 (0.4/0.6) 231.4 (0.5/0.5) 353.2
2.76 1.386 7.87 0.558 14.07 0.354
R32/R152a 4.569(1.0) . R290/R600 5.322(20SH) R12/R13 9.452(IOSH)
(0.1/0.9) 240.0 (0.1/0.9) 332.1 (0.7/0.3) 123.5
3.66 0.336 7.11 0.682 22.28 0.144
R11/R114 4.552(0.9) R134a/R143 5.313(20SH) R12/R13 9.287(1.0)
(0.9/0.1) 126.7 (0.6/0.4) 211.1 (0.6/0.4) 110.2
1.48 1.924 8.18 0.471 22.91 0.128
Table 9 The top 30 list for the highest COP, for each of the three eve s of
temperature glides. The first value in each block is the COP, (with the relevant
inlet vapour quality), the second is the specific cooling capacity (kJ/kg) and the
third is the compressor displacement per kilowatt cooling (litre/s).
53

(0°C-5°C) (5°C-10°C) (>10°C)
R11/R114 4.551(1.0) R22/R114 5.283(20SH) R22/R114 9.256(20SH)
(0.2/0.8) 106.2 (0.7/0.3) 158.5 (0.2/0.8) 148.1
2.00 1.295 9.66 0.268 19.76 0.370
R22/R134a 4.487(0.9) R124/R143a 5.254(1.0) R22/R114 9.224(1.0)
(0.8/0.2) 124.8 (0.9/0.1) 120.5 (0.3/0.7) 140.2
0.77 0.286 7.76 0.464 20.36 0.319
R12/R152a 4.452(0.9) R32/R134 5.248(0.9) R32/R124 9.204(20SH)
(0.5/0.5) 133.8 (0.1/0.9) 147.4 (0.1/0.9) -166.9
1.07 • 0.378 6.99 0.335 19.77 0.241
R32/R152a 4.421(0.9) R22/R142b 5.201(0.7) R22/R114 9.197(1.0)
(0.8/0.2) 217.6 (0.1/0.9) 104.1 (0.6/0.4) 144.7
4.62 0.176 5.35 0.61 13.32 0.272
R290/R600 4.408(20 SH) R32/R134 5.191(1.0) R123/R134a 9.168(20SH)
(0.9/0.1) 302.7 (0.5/0.5) 212.5 (0.9/0.1) 179.7
4.66 0.306 9.04 0.187 18.86 0.905
R22/R152a 4.408(1.0) R22/R124 5.188(1.0) R143/R143a 9.123(1.0)
(0.7/0.3) 186.9 (0.3/0.7) 132.8 (0.6/0.4) 237.2
2.87 0.311 7.68 0.370 20.66 0.302
R22/R152a 4.377(10SH) R32/R152a 5.157(1.0) R125/R143 9.111(10SH)
(0.8/0.2) 185 (0.4/0.6) 255.1 (0.3/0.7) 238.1
3.30 0.29 7.92 0.221 19.85 0.359
R22/R142b 4.363(1.0) R22/R124 5.130(1.0) R125/RC318 8.992(20S H)
(0.9/0.1) 155.9 (0.4/0.6) 136.8 (0.2/0.8) 111.5
2.25 0.259 7.76 - 0.336 19.53 0.27
R11/R114 4.360(1.0) R124/R125 5.110(20SH) R125/RC318 8.984(20SH)
(0.1/0.9) 99.4 (0.3/0.7) 117.2 (0.3/0.7) 112.6
1.14 1.266 9.73 0.242 19.75 0.235
R134a/R143 4.356(20SH) R32/R152a 5.110(1.0) R125/R143 8.775(1.0)
(0.9/0.1) 169.6 (0.5/0.5) 256.2 (0.7/0.3) 163.8
3.53 0.406 7.92 0.203 21.22 0.225
R12/R22 4.355(0.9) R32/R152a 5.100(1.0) R32/R142b 8.751(1.0)
(0.7/0.3) 100.9 (0.3/0.7) 252.3 (0.3/0.7) 225.2
2.94 0.316 7.31 0.247 19.45 0.217
R12/R152a 4.326(1.0) R134a/R143 5.091(20SH) R143/R143a 8.613(1.0)
(0.6/0.4) 141.9 (0.7/0.3) 198.9 (0.7/0.3) 244.6
0.35 0.359 7.43 0.442 18.98 0.353
R12/R22 4.321(10SH) R142b/R143a - 5.091(10SH) R32/R142b 8.596(0.8)
(0.8/0.2) 121.0 (0.9/0.1) 176.0 (0.2/0.8) 163.9
3.24 0.32 5.88 0.529 18.25 0.27
R22/R152a 4.299(1.0) R290/R600 5.067(20SH) R22/R114 8.454(20SH)
(0.6/0.4) 194.9 (0.8/0.2) 320.9 (0.4/0.6) 157.8
2.19 0.335 8.30 0.308 19.06 0.289
Table 9 (continued) The top 30 list for the highest COP for each of the three
levels of temperature glides. The first value in each block is the COP S (with the
relevant inlet vapour quality), the second is the specific cooling capacity (kJ/kg)
and the third is the compressor displacement per kilowatt cooling (litre/s).
54
It can be seen from Table 9 that the highest COP, (5.96(20SH)) obtained with a
low temperature glide is for R218/RC318 (0.9/0.1). R11/R114 represents 30% of
Table 9, which means that 100% of the studies conducted on R11/R114 resulted
in being tabulated in Table 9 amongst the top 30 with low temperature glides.
R12/R152a, R134a/R143 and R22/R152a all represent 10% of the entries in
Table 9.
R143/R143a (0.9/0.1) topped the chart for the medium temperature glide (5°C-
10°C) with a COP, of 6.588(0.9). R22/R142b represents 17% of the top 30 •
entries, while R134a/R143 represents 13%.
A COP, of 14.07(10SH) for R123/R134a (0.6/0.4) is the highest value obtained

in the high temperature glide (>10°C) category. R32/R143 and R125/R143 each
represents 17% of the top 30 entries, while R123/R134a and R22/R114 each
represent 13%.
Only 27% of the COP, entries in the low and medium temperature glide
categories are as a result of the process of wet compression. Only 10% of the
COP, entries in the high temperature glide category are as a result of the
process of wet compression. Dry compression dominates the chart as is
expected. Although the COP, values in Table 9 are not as spectacular as in
Table 8, they are a great improvement on the values for pure refrigerants.
3.3.2 T-s CURVE
As with pure refrigerants, non-azeotropic refrigerant mixtures can also be

divided into two groups according to the shape of their T-s curves. It was found
that the majority of non-azeotropic mixtures belong to the family with bell-
shaped curves. However, the following mixtures have T-s curves with a re-
entrant saturation vapour line: R11/R114 (for all mixture concentrations);
R123/R134a (60% to 90% R123); R124/R125 (80% and 90% R124);
R125/RC318 (10% to 50% R.125); R22/R114 (10% and 20% R22); R22/R218
(10% and20% R22); R290/R600 (for all mixture concentrations). As was found
with -pure refrigerants, none of the mixtures with re-entrant saturation vapour
line on the T-s curve produced better results with the use of wet compression.
The only mixtures that responded favourably to wet compression, came out of
the bell-shaped T-s curve family. Again, a refrigerant with a bell-shaped T-s
curve does not automatically perform better with wet compression.
55
3.3.3 DISCHARGE TEMPERATURE
The discharge temperature plays an important role in the choice of a refrigerant.

The reason for this is that the higher the discharge temperature, the more easily
the lubricant in the compressor will break down and mechanical wear of the
compressor components will accelerate. The discharge temperature was
calculated for each of the refrigerants analysed, the full details of which are
given in the Appendices.
When wet compression is used, it naturally leads to a lower discharge

temperature. Because the inlet quality is lower than 1.0, it is common for the
refrigerant mixture to discharge at a temperature very close and lower to the
dew point temperature. As an example, consider R32/R142b (0.2/0.8). The
refrigerant reaches a maximum COP S when compression takes place at a vapour
quality of 0.8. The process of wet compression leads to a discharge temperature
of 47.87°C, which is lower than the dew point temperature of 50°C. Had this
refrigerant been superheated by 10°C, the discharge temperature would have
been 72.43°C, which is approximately 26°C higher than in the case of wet
compression.
In some cases, when wet compression takes place at inlet qualities of 0.9, it is
not uncommon for the refrigerant to discharge at temperatures higher than the
dew point temperature. Even then it was found that the discharge temperature is
still much lower than the discharge temperature had dry compression been used.
It can therefor be concluded that wet compression leads to a decrease in the
discharge temperature for the few refrigerants that favour wet compression.
3.3.4 CONCLUSIONS
All the refrigerant mixtures with a re-entrant saturation vapour line on the T-s
curve produce better COP c values when the refrigerant is superheated before
entering the compressor. From the group of refrigerant mixtures with bell-
shaped T-s curves, quite a few were identified that produce better COP S values
through the process of wet compression. From Table 6, it seems that especially
R11/R114, R32/R142b, R32/R142b and R32/R143 perform better under wet
compression conditions. The use of wet compression unfortunately also results
in a drop in cooling capacity and in some cases, an increase in the compressor
displacement. It was also found that many non-azeotropic refrigerant mixtures
produce higher COP S values than pure refrigerants.
56
3.4 ENVIRONMENTAL IMPACT
Two criteria are instrumental in determining the impact a certain refrigerant has
on the environment, namely its ozone depletion potential (ODP) and its global
warming potential (GWP). Cavallini" identified a possible working region for
refrigerants after the phase-out of CFC's. This working region includes
refrigerants with an ODP of less than 0.1 (with R11 given a value of one as the
norm) and a GWP of less than 4000 (with reference to CO2, with an Integration
Time Horizon of 100 years). With the phase-out of HCFC's, this window will
shrink to a single line, which will only include refrigerants with zero ODP,
while the GWP will be limited, given the current global warming issue.
3.4.1 BEST PERFORMERS
In the light of the above-mentioned environmental restrictions, the refrigerant

mixtures in Table 9 are sorted according to three different categories in Table
10: phased—out refrigerants, temporarily accepted refrigerants and accepted
refrigerants. Temporarily accepted refrigerants refer to refrigerant mixtures
containing HCFC's. Although the phasing-out of HCFC's has already
commenced in developed countries, developing countries enjoy an extension on
the phase-out date, and therefor this group of refrigerants cannot be ignored as
yet seeing that they will probably still be used for a few decades. Due to the fact
that phased-out refrigerants are no longer in use, they should be omitted from
Table 9. For this reason Table 11 is created. Table 11 and 12 give the highest
COP c performers for respectively temporarily acceptable refrigerants and
acceptable refrigerants.
Phased-out refrigerant Temporarily acceptable Acceptable refrigerant

mixtures refrigerant mixtures mixtures
R1 1/R114 R22/R124 R32/R134a
R12/R22 R22/R134a R32/R143
R12/R152a R22/R142b R32/R152a
R13b1/R152a R22/R152a R125/R143
R22/R114 R32/R124 R125/RC318
R123/R134a R134a/R143
R124R125 R134a/R143a
R124/R143a R143/R143a
R125/R142b R218/RC318
R142b/R143a R290/R600
Table 10 The three categories of refrigerant mixtures of Table 9 identified in

the light of the environmental restrictions
57
Temporarily acceptable refrigerant mixtures

(0°C-5°C) (5°C-10°C) (>10°C)
R22/R134a 4.890(0.9) R22/R142b 6.056(20SH) R123/R134a 14.07(10SH)
(0.7/0.3) 123.8 (0.3/0.7) 195.4 (0.6/0.4) 191.4
1.15 0.295 9.97 0.368 26.98 0.44
R22/R124 4.887(0.9) R22/R142b 5.880(0.9) R123/R134a 13.24(10SH)
(0.1/0.9) 103.1 (0.6/0.4) 153.4 (0.8/0.2) 185.3
4.45 0.539 9.01 0.291 25.26 0.614
R22/R134a 4.487(0.9) R142b/R143a 5.871(0.9) R123/R134a 11.84(20SH)
(0.8/0.2) 124.8 (0.8/0.2) 149.7 (0.5/0.5) 197.3
0.77 0.286 9.54 0.438 25.05 0.407
R22/R152a 4.408(1.0) R22/R142b 5.709(0.7) R32/R124 9.827(1.0)
(0.7/0.3) 186.9 (0.2/0.8) 109.7 (0.2/0.8) 166.4
2.87 0.311 8.39 0.482 21.07 0.187
R227R152a 4.377(10SH) R125/R142b 5.638(20 SH) R123/R134a 9.700(20SH)
(0.8/0.2) 185 (0.2/0.8) 177.4 (0.4/0.6) 192.7
3.30 0.29 9.03 0.443 21.91 0.390
R22/R142b 4.363(1.0) R22/R143 5.531(0.9)21 R32/R124 9.204(20SH)
(0.9/0.1) 155.9 (0.1/0.9) - 2.3 ' (0.1/0.9) 166.9
2.25 0.259 6.83 0.698 19.77 0.241
R22/R152a 4.299(1.0) R124/R125 5.431(20SH) R123/R134a 9.168(20SH)
(0.6/0.4) 194.9 (0.8/0.2) 131.8 (0.9/0.1) 179.7
2.19 0.335 8.59 0.399 18.86 0.905
Table 11 The highest COP, values for each of the three levels of temperature
glides, considering only temporarily acceptable refrigerant mixtures. The first
value in each block is the COP, (with the relevant inlet vapour quality in
brackets), the second is the specific cooling capacity (kJ/kg) and the third is the
compressor displacement per kilowatt cooling (litre/s)
It can be seen that Table 11 only has seven entries. The reason for this is that
out of the 30 entries in Table 9, only 7 entries are temporarily acceptable from
an environmental perspective, considering low and high temperature glides.
From Table 11, it seems that for respectively low and medium temperature glide
mixtures, R22/R134a (0.7/0.3) and R22/R142b (0.3/0.7) provide medium term
solutions. Obviously R22/R142b is chosen above R22/R134a seeing that its COP
is 24% and its specific cooling capacity 58% higher than the same values of
R22/12.134a. Unfortunately, though, the required compressor displacement rate
increased by 25%.
Comparing high with medium temperature glide, the COP, value of 14.07
recorded for R123/R134a (0.6/0.4) is more than double . than the COP, of
R22/R142b. Unfortunately, for R123/R134a, the required compressor
displacement rate is 20% higher, and the specific cooling capacity 2% lower.
58
Acceptable refrigerant mixtures

(0°C-5°C) (5°C-10°C) (>10°C)
Ft218/RC318 5.96(20SH) R143/R143a 6.588(0.9) R32/R143 13.0(0.8)
(0.9/0.1) 60.9 (0.9/0.1) 215.9 (0.3/0.7) 238.1
2.78 0.398 9.94 0.611 25.85 0.235
R125/R143a 5.087(20SH) R125/R143 5.873(1.0) R32/R143 12.69(1.0)
(0.8/0.2) 103.1 (0.1/0.9) 239.6 (0.4/0.6) 308.0
0.08 0.238 9.64 0.615 26.42 0.198
R134a/R143 4.735(20SH) R32/R134 5.630(1.0) R32/R143 11.43(1.0)
(0.3/0.7) 237.4 (0.2/0.8) 185.4 (0.5/0.5) 306.4
4.26 0.690 9.75 0.255 25.42 0.179
R32/R142b 4.712(0.9) R134a/R143 5.382(1.0) R32/R143 10.93(0.8)
(0.8/0.2) 209.0 (0.5/0.5) 203.8 (0.2/0.8) 229.6
6.90 0.169 8.35 0.512 22.94 0.297
R134a/R143, 4.652(0.9) R134a/R143 5.356(20SH) R125/R143 10.58(20S1E1)
(0.1/0.9) 203.5 (0.4/0.6) 231.4 (0.5/0.5) 221.4
3.07 0.845 7.87 0.558 23.31 0.264
R32/R152a 4.569(1.0) R290/R600 5.322(20SH) R125/R143 10.58(20SH)
(0.1/0.9) 240.0 (0.1/0.9) 332.1 (0.6/0.4) 221.4
3.66 0.336 7.11 0.682 23.01 0.264
R32/R152a 4.421(0.9) R134a/R143 5.313(20 SH) R125/R143 10.19(1.0)
(0.8/0.2) 217.6 (0.6/0.4) 211.1 (0.4/0.6) 217.4
4.62 0.176 8.18 0.471 22.23 0.302
R290/R600 4.408(20SH) R32/R134 5.248(0.9) R32/R143 9.689(1.0)
(0.9/0.1) 302.7 (0.1/0.9) 147.4 (0.6/0.4) 301,0
4.66 0.306 6.99 0.335 23.2 0.167
R134a/R143 4.356(20SH) R32/R134 5.191(1.0) R290/R600 9.461(20SH)
(0.9/0.1) 169.6 (0.5/0.5) 212.5 (0.5/0.5) 353.2
3.53 0.406 9.04 0.187 14.07 0.354
R32/R152a 5.157(1.0) R143/R143a 9.123(1.0)
(0.4/0.6) 255.1 (0.6/0.4) 237.2
7.92 0.221 20.66 0.302
Table 12 The highest COP, values for each of the three levels of temperature
glides, considering only acceptable refrigerant mixtures. The first value in each
block is the COP, (with the relevant inlet vapour quality in brackets), the
second is the specific cooling capacity (kJ/kg) and the third is the compressor
displacement per kilowatt cooling (litre/s)
From Table 12, it seems that concentrations of R290/R600 possess the best
combination of the thermodynamic characteristics. It provides both a high COP,
as well as a high specific cooling capacity. Unfortunately this mixture carries a
high risk of flammability (see later the paragraph on flammability and toxicity).
R32/R152a, at an inlet quality of 1.0, is chosen as the long-term solution in the

low and medium categories. In the low temperature glide category R32/R152a
(0.1/0.9), and R32/R152a (0.4/0.6) in the medium temperature glide category,
have the highest specific cooling capacities apart from R290/R600. R32/R152a
59
(0.4/0.6) has the lowest compressor displacement per kilowatt cooling in the
medium temperature glide category.
In the high temperature glide category, R32/R143 (0.4/0.6) at an inlet quality of

1.0, has the second highest specific cooling capacity of 308.0 kJ/kg. It also has
the lowest required compressor displacement rate of 0.198 1/s and a high COP °
value of 12.69.
To summarise: the temporarily acceptable mixtures with the best combination of

high COP C and cooling capacity are R22/R134a (0.7/0.3) for low, R22R14'2b
(0.3/0.7) for medium and R123/R134a (0.6/0.4) for high temperature glide
categories. The long-term acceptable refrigerant mixtures are R32/R152a
(0.1/0.9) for low, R32/R152a (0.4/0.6) for medium and R32/R143 (0.4/0.6) for
high temperature glide categories.
3.4.2 WHAT ABOUT R123?
In the discussion of the impact refrigerants have on the environment, R123 has
been identified as a temporarily acceptable refrigerant. This is because R123 is
a HCFC that is, under the Montreal Protocol, scheduled-for phase-out with the
rest of the HCFC's currently in use. R123, unlike the majority of HCFC's has
both a low GWP (Global Warming Potential) and ODP (Ozone Depletion
Potential). R123 has an atmospheric lifetime of 1.4 years, which gives a virtual
guarantee that no R123 would possibly enter the stratosphere. Also, it has been
shown 2° that under certain conditions, the use of R123 has a negligible impact
on the ozone layer. This has led to some controversy in the US air-conditioning
industry over the Protocol grouping of all HCFC's under one blanket. This, and
the fact that R123 is regarded in some circles as still the best alternative for
R112, may put some pressure on authorities to rethink the phase-out of R123.
Should this happen, R123 will remain an important role player in the heating,
ventilation and air-conditioning industry in future.
3.4.3 FLAMMABILITY AND TOXICITY
In order to evaluate refrigerants on a common basis regarding flammability and

toxicity, use was made of the ASHRAE 34-1992 Standard 2 `. Flammability is
tested according to the American Society of Testing Materials (ASTM) E-681
and the refrigerant is assigned to one of three catego'ries: 1 — no flame
propagation, 2 — low flammability or, 3 — high flammability. For example, under
ASHRAE 34-1992, R125 is classified in group 1, no flame propagation, because
it is not flammable at any concentration in air at atmospheric pressure. For
toxicity, there are two classifications: "A" and "B". The "A" designates lower
60
toxicity and the "B" higher toxicity. These designations are applied with the
numbers of flammability to complete the safety classification. For example: R22
is classified Al, no flame propagation, lower toxicity; NH 3 (R717) is classified
B2, low flammability, higher toxicity.
For refrigerant mixtures, the classification is rather more complex. For example,
the mixture might have one classification as it is purchased, but should the
components separate, this classification can change. For this reason the
refrigerants in Tables 10 to 12 were classified according to the original
components. From the refrigerant components in these tables the majority was
classified Al and A2. The only exceptions were R123 (B1), R290 (A3) and R600
(A3). For this reason, note should be taken of the hazards presented by mixtures
of R123/R134a and R290/R600, as identified in Tables 10 to 12.
61
CHAPTER FOUR
62
4. SUMMARY, CONCLUSIONS AND RECOMMENDATION

4.1 SUMMARY
The purpose of this study was to determine the effect of wet compression on the
performance of a wide variety of pure refrigerants and refrigerant mixtures. A
total of 34 pure refrigerants and 31 binary refrigerants were analysed. The
binary refrigerant mixtures were analysed at mass ratio intervals of 10%, which
brought the total number of mixtures analysed at almost 300. To determine the
effect of wet compression on these refrigerants, the cooling coefficient of
performance, specific work done by the compressor, specific cooling capacity,
refrigerant circulated and the compressor displacement rate were calculated at
different inlet qualities. These qualities ranged from a vapour quality of 0.3 to
one at 0.1 intervals, and for 10°C and 20°C superheat.
Each refrigerant was analysed purely on a theoretical basis, with the

thermodynamic properties calculated using a computer database. One
application, namely that of air conditioning was considered. For this application
an evaporation temperature of 7°C and a condensing temperature of 50°C were
used.
4.2 CONCLUSIONS
After analysing the 34 pure refrigerants it was concluded that all of them can be
divided into two distinctive groups, depending on the shape of their temperature
entropy curves. Two common shapes were identified: a bell shape and a re-
entrant curve. From the 34 pure refrigerants analysed, all those with re-entrant
saturated vapour lines produce better COP,'s when the refrigerant is superheated
before entering the compressor. Only two of the refrigerants (R32 and NH3) with
bell-shaped T-s curves, consistently produce higher COP c 's when wet
compression is used. It can therefore be concluded that in general it has been
found that wet compression is not attractive when pure refrigerants are used.
Reviewing the binary non-azeotropic mixtures analysed, it seems from a COP,

point of view that for air conditioning, the following refrigerant mixtures
consistently respond favourably to wet compression: R11/R114, R12/R22,
R124/R125, R142b/R143a, R143/R143a, R22/R134a, R22/R142b,
R22/R152a, R22/R218, R32/R124, R32/R125, R32/R134, R32/R143,
R32/R152a, R32/R42b, R22/R124, R22/R143 and R134a/R124. As with pure
refrigerants, the specific cooling capacity decreases and the compressor
displacement increases with the use of wet compression as can be expected. It
was found, however, that for some refrigerant mixtures, for example R32/R143
(0.3/0.7), the compressor displacement reaches a relative low value at
approximately the same vapour quality where the maximum COP, is reached. it
63
is interesting to note that this phenomenon occurs especially in refrigerant

mixtures that produce higher COP, values with wet compression. It is
recommended that this phenomenon be investigated more closely. The opposite
also seems true: refrigerant mixtures for which the compressor displacement
decreases when it is superheated, do not tend to enjoy the advantages of wet
compression. It was found that only 1.1% of all the refrigerant mixtures
considered produced higher COP, through the process of wet compression.
It was also found that the temperature glide of each refrigerant mixture plays, an
important role in how it will perform. It was possible to define an accurate
approximation of the COP, as a function of the temperature glide for all the
refrigerant mixtures considered. The approximation has an average error of 7%.
The refrigerant mixtures were grouped into three different temperature glide
categories, depending on its type of temperature glide distribution. The highest
COP, obtained with a low temperature glide was for R218/RC318 (0.9/0.1).
R143/R143a (0.9/0.1) topped the chart for the medium temperature glide whilst
R123/R134a (0.6/0.4) out performed the rest in the high temperature glide
category. Although the COP, values were not so spectacular, they are a great
improvement on the values for pure refrigerants.
As with pure refrigerants, non-azeotropic refrigerant mixtures were also divided

into two groups according to the shape of their T-s curves. All the refrigerant
mixtures with a re-entrant saturation vapour line on the T-s curve produced
better COP, values when the refrigerant was superheated before entering the
compressor. From the group of refrigerant mixtures with bell-shaped T-s curves,
quite a few were identified that produce better COP, values through the process
of wet compression. It seemed that especially R11/R114, R32/R142b,
R32/R142b and R32/R143 performed better under wet compression conditions.
The use of wet compression unfortunately also resulted in a drop in cooling
capacity and in some cases, an increase in the compressor displacement. Again,
a refrigerant with a bell-shaped T-s curve did not automatically perform better
with wet compression. To conclude, mention was made of the advantages of wet
compression on the discharge temperature and the effect it hai on compressor
1i
The impact of the refrigerants on the environment was also taken into account.
Three types of refrigerants were identified: phased-out refrigerants, refrigerants
that are temporarily acceptable and acceptable refrigerants. With the phased-out
refrigerants ignored, the temporarily acceptable mixtures with the best
combination of high COP, and cooling capacity were R22/R134a (0.7/0.3) for
low, R22/R142b (0.3/0.7) for medium and R123/R134a (0.6/0.4) for high
temperature glide categories. R22/R134a was compressed at a vapour quality of
0.9, R22/R142b at 20SH and R123/R134a at 10SH.
64
The long-term acceptable refrigerant mixtures were R32/R152a (0.1/0.9) for

low, R32/R152a (0.4/0.6) for medium and R32/R143 (0.4/0.6) for high
temperature glide categories. All three refrigerants were compressed at a vapour
quality of 1.0.
The top performing refrigerant mixtures were also evaluated for flammability
and toxicity using the ASHRAE 34-1992 Standard. Only mixtures of
R123/R134a and R290/R600 were identified as exceptional hazards regarding
flammability and toxicity.
A final look at the top performing refrigerant mixtures revealed that only 27%
of the refrigerant mixtures in the low and medium temperature glide categories
prefer the process of wet compression. Only 10% of the refrigerant mixtures in
the high temperature glide category prefer the process of wet compression.
Non-azeotropic mixtures tend to gain more from wet compression than pure
refrigerants when considering the COP c values. Unfortunately, though, the
cooling capacities decrease in general. Another advantage of some of the non-
azeotropes is that the compressor displacement does not necessarily increase
substantially when wet compression is applied.
4.3 RECOMMENDATION
It is recommended that a computer program, similar to REFPROP, should be

developed that is more easily accessible, consumer friendly and assessable. It is
also recommended that this program should be compatible with all modern day
computer programs„ such as Microsoft Windows and Microsoft Office. With
such a program it would be possible to evaluate all the refrigerant mixtures at
all possible concentrations. It will also be much easier to perform calculations
with the relevant data as well as writing a report. It could be expected that many
mixtures would be discovered that would perform better that the mixtures
identified in this study.
65
REFERENCES
66
Rowland, F.S. Stratospheric ozone depletion: identifying the problem and the solution,
ASHRAE Journal, (September 1997), pp. 29-31
Cavallini, A. Working fluids for mechanical refrigeration, International Journal of
Refrigeration; (1996) 19(8), 485-496
Lorentzen, G. The use of natural refrigerants: a complete solution to the CFC/HCFC
predicament, International Journal of Refrigeration, (1995) 18(3), 190 197
-
Richardson, R.N., Butterworth, J.S. The performance of propane/isobutane mixtures in a

vapour-compression refrigeration system, International Journal of Refrigeration (1995) 18(1),
58-62
Rane, M.V., Radermacher, R. Feasibility study of a two stage vapour-compression heat
pump with ammonia-water solution circuits: experimental results, International Journal of
Refrigeration , (1993) 16 (4), 258-264
Sand, J.R., Fischer, S.K. Screening analysis for chlorine-free alternative refrigerants to
replace R-22 in air-conditioning applications, ASHRAE Technical Data Bulletin, (1993) 9(4), 12-
20
Domanski, P.A., Didion, D.A. Thermodynamic evaluation of R-22 alternative refrigerants
and refrigerant mixtures, ASHRAE Technical Data Bulletin, (1993) 9(4), 21-33
Kondepudi, S.N. Drop-in testing of R-32 blends as R-22 alternatives in a split-system air
conditioner, ASHRAE Technical Data Bulletin (1993) 9(4), 40-47 -
Sanvordenker, K.S. Experimental evaluation of an R-32/R-134a blend as a near drop-in
substitute for R-22, ASHRAE Technical Data Bulletin (1993) 9(4), 34-39
Spatz, M.W., Zheng, J. R-22 Alternative refrigerants: performance in unitary equipment,
ASHRAE Technical Data Bulletin (1993) 9(4), 48 54-
Linton, J.W., Snelson, W.K., Hearty, P.F., Triebe, A.R. System performance of near
azeotropic mixtures of R-134a and R-152a , ASHRAE Technical Data Bulletin, (1993) 9(4), 55-
60
Radermacher, R., Jung, D. Theoretical analysis of replacement refrigerants for residential
uses, ASHRAE Technical Data Bulletin (1993) 9(4), 1 11
-
Stoecker, W.F., Jones, J.W. Refrigeration and Air Conditioning, McGraw Hill, 3rd ed.
-
(1982) 193-195
Itard, L.C.M. Wet compression versus dry compression in heat pumps working with pure
refrigerants or non-azeotropic mixtures, International Journal of Refrigeration (1995) 18(7) 495,
504
MST REFPROP Standard Reference Database 23. MST Thermodynamic properties of
refrigerants and refrigerant mixtures Version 4.0, Thermophysics Division, National Institute of
Standards and Technology, (November 1993) Gaithersburg, MD 20899
Kruse, H., Kuever, M., Guast, U., Schroeder, M., Upmeier, B. Theoretical and
Experimental Investigations of Advantageous Refrigerant Mixture Applications, ASHRAE
Technical Data Bullitin (1985), 96 131
-
Nagel, M., Bier, K. Vapour-liquid equilibrium of ternary mixtures of the refrigerants R32,
R125, and R134a, International Journal of Refrigeration, (1995), 18(8), 534 543
-
Cavallini, A. CFC and HCFC substitution — short-and long-term solutions, IIR Bulletin,
(1994), 94(6), 2-15
Calm, J.M., Didion, D.A. Trade-offs in refrigerant selections: past, present and future
Refrigerants for the 21st Century (1997), 6-19
67
Sanvordenker, K.S. Status of CFC and HCFC alternatives Refrigerants for the 21st Century
(1997), 111-116rade-offs in refrigerant selections: past, present and future
ASHRAE Standard 34-1992 Number Designation and Safety Classification of Refrigerants,
American Society of Heating, Refrigeration and Air-Conditioning Engineers, Inc., Atlanta, GA,
USA (1992), 1-9

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WET COMPRESSION VERSUS DRY COMPRESSION IN

REFRIGERATION CYCLES WORKING WITH PURE OR NON-

submitted in partial fulfilment of the

requirements for the degree

RAND AFRIKAANS UNIVERSITY

STUDY LEADER: PROF J.P. MEYER

Wet compression versus dry compression in refrigeration cycles working with

CONTRIBUTIONS OF THIS STUDY

A total of 34 pure refrigerants were analysed for a commonly known

A total of 31 binary non-azeotropic refrigerant mixtures were analysed at

In both the evaluations of pure refrigerants and non-azeotropic mixtures, the

Figure I A comparison between the evaporation and condensation temperatures of a pure

Temporarily acceptable refrigerant mixtures

Acceptable refrigerant mixtures

All the refrigerants, pure and non-azeotropic, could be divided into

Entropy [kJ/kg.K] Entropy [kJ/Icg.K]

The majority of non-azeotropic mixtures belong to the family with

Non-azeotropic refrigerant mixtures tend to gain more from wet

PART I: PURE REFRIGERANTS 8

PART II: NON-AZEOTROPIC REFRIGERANT MIXTURES 21

3.4 ENVIROMENTAL IMPACT 56

4. SUMMARY, CONCLUSIONS AND RECOMMENDATION 62

COPe Coefficient of performance for cooling

hf Specific enthalpy at saturated liquid qualities (J kg -I )

hg Specific enthalpy at saturated vapour qualities (J kg -I )

Refrigerant mass flow for each kilowatt of cooling (kg s -I )

q Specific cooling capacity (J kg -I )

s Specific entropy (J kg -1 K -I ) or isentropic point in figures

Tcond Condensation temperature (K)

Tevap Evaporation temperature (K)

Tg TeMperature glide (K)

V Compressor displacement rate for each kilowatt of cooling (m 3 s-1)

p Refrigerant density (kg m 3 )

Tic Compressor isentropic efficiency

The Montreal Protocol is an international agreement designed to protect the

The Montreal Protocol stipulates that the production and consumption of

Evaporation and condensation of a non-azeotropic mixture takes place at non-

The compression process 13 , 1' to 2', in Figure 2 is called wet compression

Because of the current practical problems with wet compression, dry

1.2 PREVIOUS WORK

Itard 14 investigated wet compression versus dry compression in heat pumps

1.3 PURPOSE OF THIS STUDY

It is the purpose of this paper to consider more refrigerants- 34 pure refrigerants

For this type of study, accurate thermodynamic refrigerant properties are

1.4 SCOPE OF THIS STUDY

2. PART I: PURE REFRIGERANTS

R11 Trichlorofluoromethane R12 Dichlorodifluoromethane

2.2 CYCLE ANALYSIS

The performance of the different refrigerants for air conditioning applications

w = hr- hi. (2)

The value of hl' is calculated on the evaporating pressure line as

hi .(x)= hr + x(hg - h r) (3)

The specific cooling capacity for dry compression is calculated as

while the specific cooling capacity for wet compression is calculated as

The cooling coefficient of performance for dry compression is

COP = (hi - ha)/(h2 -

The cooling coefficient of performance for wet compression is calculated as

COP = (h• -114)/(hr- hi•) (7)

V= (1/(h i - h4 ))p *1000 (10)

V= (1/(h• - h4 ))p *1000 (11)

Figures 3 to 6. The .three different refrigerants used in this comparison, E245,

Reviewing the results for refrigerants circulated (Figure 5) and compressor

2.3.2 SUMMARY OF RESULTS