&EPA
             United States
             Environmental Protection
             Agency
             Air And
             Radiation
             (ANR-445)
EPA/400/1-91/041
January 1992
Theoretical Analysis of
Replacement Refrigerants
for R22 for Residential Uses

                         * ~,»_:
                         -,?SP. _^9» Printe^ on Recycled Paper
                         $«a ^•ymTl.-.*.* >•?«£<. ~ 4 *-• •• - --

-------

-------
THEORETICAL ANALYSIS! OF REPLACEMENT REFRIGERANTS FOR R22

                  FOR RESIDENTIAL USES


                      Prepared for
           US Environmental Protection Agency
                 Global Change Division
     Office  of Atmospheric and Indoor Air Programs
              Office of Air and Radiation
                           by

        Reinhard Radermacher and  Dongsoo Jung
          Department of Mechanical Engineering
               The University of Maryland
             College Park,  MD 20742-3035
                     December 1991

-------

-------
                        Table of Contents

List of Exhibits	    3

Abstract	i  .......    4

Findings	    5

1.0  Background and Objective	    7


2.0  Simulation Approach	    11
     2.1   Computer Model	    11
     2.2   Refrigerant Properties   	  	    15
     2.3   Refrigerant Mixtures	    15
     2.4   Operating Conditions	    17
     2.5   Capacity Modulation with Mixtures  	    19

3.0  Seasonal Performance Evaluation  	  	    21

4.0  Results and Discussions	    29
     4.1   Performance Under Design Conditions  	    29
     4.2   Seasonal Performance	    37
     4.3   Concentration Shift	    40
     4.4   Drop-in Application vs.  New Systems	    44
     4.5   Implications of Counter-flow Design and the Use of
          Mixtures  .... *	    45
     4.6   Sensitivity Considerations and Accuracy 	    46
     4.7   Global Warming Potential (GWP) and Ozone Depletion
           Potential (ODP)	    48

5.0  Flammability and Materials Compatibility  	 .    51
     5.1   Flammability	    51
     5.2  Materials Compatibility 	    52

6.0  Further Work	    54
                     '
References	    55

Appendices                                     \

-------
                         List  of  Exhibits
Exhibit  1:   Total Clx Concentrations (1985-2000).  .   .   .   .8
Exhibit  2:   Greenhouse Warming Potential of R22 and Other
     HCFC's and Carbon Dioxide	9
Exhibit 3:    Sample Printout of Computer  Run with HAC1.   .   . 14
Exhibit 4:    Fractional Temperature Bin Hours for Six Heating
     Climates of the Continental US.   ...   	
Exhibit 5:    Map of the US Displaying Lines of Constant
     Cooling Load Hours	
Exhibit 5a:   Map of the US Displaying Lines of Constant
     Cooling Load Hours	
Exhibit 6:    Sample Seasonal Performance  Calculation.
Exhibit 7:    Cooling and Heating COP and Volumetric Capacity
     for Binary Refrigerant Mixtures.  .........
Exhibit 8:    Cooling and Heating COP and Volumetric Capacity
     for Binary Refrigerant Mixtures.  .   .   .   .   .   • '  •
Exhibit 9:    Cooling and Heating COP and Volumetric Capacity
     for Binary Refrigerant Mixtures	
Exhibit 10:   COP of Mixtures in Sequence According to Their
     Performance	
Exhibit lOa:  Best Substitutes for R22.  .  .   	
Exhibit 11:   Seasonal Performance of R22 and the Five Best
     Replacements for One Cooling and Six  Heating Climates.  .  .
Exhibit 12:   Seasonal Performance Factors  (SPF) for One
     Cooling and Six Heating Climates	
Exhibit 13:   Ratio of Heating Capacities	
Exhibit 14:   Seasonal Performance of R32/R152a and R32/R124
     With  and Without a Rectifier	
Exhibit 15:   Greenhouse Warming  (100 yr. Horizon) and Ozone
     Depletion Potential	
Exhibit 16:   Direct and Indirect Contributions to Global
     Warming	«	
23


25


26
28

31


32


33


35
36


39


40
41

43


49


50

-------
     THEORETICAL ANALYSIS OP REPLACEMENT REFRIGERANTS FOR R22

                       FOR RESIDENTIAL USES



                             Abstract
Future  risks  of stratospheric ozone depletion and the  relatively
high  global warming  potential of  R22  might  eventually  lead to
further limitations  on  the  use  of  R22  in  heat pump  and air-
conditioning systems.  This report investigates the feasibility of
replacement refrigerants that would cause the  least disruption to
current technology.   It is  desirable that any  substitute is at
least as energy efficient  as  R22 so  that  the indirect effect on
global  warming  does  not  outweigh  the direct effect.   To date, no
acceptable  pure  component  has  been  identified as   a  drop-in
substitute for R22.   However,  binary and ternary mixtures appear to
be candidates that warrant further investigation.
     The  coefficient  of  performance  (COP)  and  the  seasonal
performance factor (SPF)  were calculated in a  model for binary  and
ternary substitutes.  The ternary  mixture of R32/Rl52a/R124 showed
the best performance  with  an  increase in  COP of 13.7 % over R12.
The best  chlorine-free  ternary mixture is R32/R152a/R134 with a
12.6  %  increase.    The  best  chlorine-free  binary  mixture  is
R32/R152a with  a 12.1 %  improvement in  COP over R22.   The binary
mixture of R32/R134a shows a performance improvement of six percent
over R22.  Since it contains  70 % R134a it may not be flammable.
     Significant design changes to the system  will be necessary to
realize all  these  gains  with  mixtures,  likely  requiring  a
considerable research and development effort.  Some of the design
changes  could  reduce the  energy  savings.    On  the other hand,
modelling predicts that the SPF can be improved by modulating the
capacity by changing mixture concentration.
     The greenhouse warming potential of the  R32/R152a/R124 mixture
and its ozone depletion potential are  reduced by a factor  of 5
compared  to   R22.      The   greenhouse   warming  potential   of
R32/R152a/R134 is reduced by a factor  of 3 compared to R22 and the
ozone  depletion  potential  is zero.    The  greenhouse  warming
potential of R32/R152a is reduced  by a factor of 6 compared to R22
and the ozone depletion potential  is zero.
     In practice,  the ranking  of the substitutes presented in this
report may change due to  the influence of transport properties and
other variables which have  been ignored in the model.

-------

-------
THEORETICAL ANALYSIS OF REPLACEMENT REFRIGERANTS FOR R22

                  FOR RESIDENTIAL USES


                        Findings

Evaluation of R22 substitutes has to occur because of concerns
about ozone depletion and greenhouse warming  effect.

There is  currently no  pure  fluid that is considered to be  a
suitable  drop-in  substitute  for R22.
                                           i

Any  substitute  should  seek  to have at least the same  energy
efficiency  as  R22.  Otherwise,  the  indirect global warming
effect  may  offset  any  gains in the  reduced global warming
potential of   the substitute.    Selection  of  the   final
substitute should consider a balanced trade-off between  direct
and  indirect global warming effect, ozone depletion  and other
health  and safety concerns.

There are several binary and ternary mixtures  of refrigerants
that warrant further investigation as substitutes for  R22.

Models predict that a mixture  containing R32 and  R152a and R32
and   R124  show   potential  for  significant   performance
improvements of up to  13J7  % in COP  over R22 in residential
air-conditioners,  heat pumps  and window air-conditioners.

Hardware  changes   (counter-flow  heat exchangers)   will  be
necessary to achieve this improvement and requirements like
increased fan power may offset the predicted energy savings.

The most energy  efficient replacement mixture, R32/R152a/R124,
as predicted by modelling, has a global warming potential and
ozone depletion potential that  is  five  times lower than the
values  for R22  (based on a 100 year time horizon).

The  replacement mixture with  the  least  direct impact on the
environment is R32/R152a with a global warming potential that
is  six  times  lower than for  R22 and  an  ozone  depletion
potential of zero.  Its predicted COP is 12.1% above that of
R22.

The ranking of the substitutes may change due*  to the influence
of transport properties and  other variables not considered in
this report.

The  use of mixtures offers  the  potential advantage that the
concentration can  be shifted  to  meet  capacity requirements.
This can lead to a reduction  in resistance heat and increased
seasonal  performance.

-------
     For some  superior mixtures  all  constituents are  presently
     available  or have  been  commercially produced;  for  other
     alternatives they will be available in the  near  future;  for
     some alternatives they are not yet  scheduled for commercial
     production.

     The mixtures with the most significant improvement in COP are
     flammable (R32/R152a) or contain flammable components so that
     they  may  be  flammable  (R32/R152a/R124,   R32/R152a/R134).
     However,   it  is  expected  that  the  addition  of  a  third
     nonflammable component will reduce the fire hazard.

     The binary mixture of  30%  R32 and 70% R134a  shows a  six
     percent  performance   improvement   over   R22  and   may   be
     nonflammable.

     Further work in the following areas is required  in  order to
     facilitate the use of the proposed mixtures:

               Materials compatibility,
               Flammability,
               oil compatibility,
               Compressor life,
               Chemical stability,
               Thermodynamic properties,
               Transport properties,
               Performance in actual cycles,
               Design of means for concentration shift,  and
               Redesign of air-conditioning and heat pump systems.

     The possibility still exists  that pure fluids can be found or
     developed that may be acceptable substitutes for R22.
                         Acknowledgement

The authors  thank the numerous  reviewers and EPA  personnel  for
constructive criticism and their contributions to the report.  The
support of this project by the US Environmental Protection Agency
through  ICP  Inc.  and  the University  of Maryland  is  greatfully
acknowledged*

-------
     THEORETICAL ANALYSIS OP REPLACEMENT REFRIGERANTS FOR R22

                       FOR RESIDENTIAL USES


1.0  Background and Objective

R22 is widely used as a refrigerant in commercial refrigeration and

commercial and residential air-conditioning and heart pumping.   R22
                                                j
has favorable thermodynamic and transport properties and well known

material compatibility characteristics.
                                                I
     However,  questions  have  been  raised  about  the  long  term

viability of R22.   Its ozone depletion potential is 0.05, much  less

than Rll or R12.   But because  the level of stratospheric chlorine

is expected to  rise during the next decade,  Exhibit 1, extensive

use of  R22 could  contribute  to  surplus chlorihe  and  thus ozone

depletion for a long time.  In Exhibit 1,  the  area enclosed between
                                                I

the two curves  is a  measure for the  increased long term risk if

there is an additional amount of Clx available in the stratosphere.

Currently, scientists are concerned that additional chlorine will

cause significant  ozone depletion /!/.  If it does, there will be

inevitably calls  for more  stringent reductions in R22  than those
                                                i
recorded during the London revisions of the Montreal Protocol where
                                                !
a resolution was passed to phase out use in new machinery by 2015

or those proposed  in the Clean Air Act revisions /2/.

     Furthermore,  the greenhouse  warming  potential  of R22 is quite

high compared to  carbon dioxide, the most important green house

gas.   The United Nations  Intergovernmental Panel  on Climate Change

(IPCC)  has published a                          !

-------
ve]
    €>J

    If)
    CO
 X
U4
     O
    O
    o
    IS
    15
                                                             O
                                                             O
                                                             o
                                                             CM
                                                             §.
                                                             0)
pe
ductions
                                        8

























CO
a.
E
CO
CO
o
ei>
CO
CO
JC
CL
"c5
.fi
O
O
E


"8
mm
!E
O

>1
flj


c
CO
0>
•—
o
o
o
PCs, Carbon Tetra
o



o>
o>
T-


c
"5>
CD
•Q
CO
o
c
0
o
E
s
B
o
z
0
_l
5*
*•*
0)
•o
m
%v
0)
•o
arbon Tetracholorj
o



c
O
u_
O

"S
^5
CM
CO
^
-Q
0)
+•>
3
1

CO
2
(0
m
o
d
"S
Q.
Q
O
0)
D)
CO
CFCs with an aver
n
•














o
CO
o
CM
C
4ntf

9
CD
1
Q.
a w\
to
O
CM
C.
CFC global freeze
X
•


                                                                                     u.
                                                                                     o

                                                                                     o
                                                                                     o>
                                                                                     o>
                                                                                     I

-------
                               Exhibit 2:
Greenhouse Warming Potential of R 22 and Other HCFC's and Carbon Dioxide
Fluid
Carbon Dioxide
Methane-inc indirect
Nitrous Oxide
CFC-11
CFC-12
HCFC-22
HFC-32*
CFC-113
CFC-11 4
CFC-11 5
HCFC-123
HCFC-124
HFC-125
HFC-134a
HCFC-141D
HCFC-142b
HFC-1433
HFC-1523
CC14
CH3CC13
CF3Br
Gtobal Warming Potential
Integration Time Horizon, Years
20
1
63
270
4500
7100
4100
2040
4500
6000
5500
310
1500
4700
3200
1500
3700
4500
510
1900
350
5800
100
1
21
290
3500
7300
1500
560
4200
6900
6900
85
430
2500
1200
440
1600
2900
140
1300
100
5800
500
1
9
190
1500
4500
I
510
188
2100
5500
7400
29
150
860
420
150
540
1000
47
460
34
3200
  Reference /3/



 report  in which the higher greenhouse wanning potential  (GWP) of


 R22 is compared for different time periods to other HCFCs,  HFCs and
                                                 i

 to carbon dioxide, Exhibit 2.  As concern about the global warming


 heightens, the availability of R22 could be threatened.  Its price
                                                 !
                                                 i
 could rise if "greenhouse gas taxes" are passed  or if green house


 gases  are limited  in  an allowance system  under a comprehensive

-------
approach such  as that  proposed  by the US  at the  first climate
negatiations.   (A tax  as small  as  $ 0.01  per pound  of  carbon
dioxide would result in an increase of  $ 15.00 per pound using the
100 year equivalent global warming potential.)
     However, it  is  important to recognize that for  HCFC  22 the
global  warming potential  is  relatively  small  compared  to the
indirect global warming effect caused by the production of carbon
dioxide to provide the power  for  air-conditioning or heat pumping.
Estimates  indicate  that up  to 10% of the total  global warming
caused by a typical air-conditioner is contributed by R22 /3/.  Any
replacement must, therefore,  be  at least as  efficient  as  R22 in
order to achieve a significant net reduction in the global warming
effect.
     Currently no pure fluid drop-in replacements for R22 have been
identified.     Refrigerant   mixtures   of   already   available  or
identified constituents,  however,  may be able to  replace  R22 in
existing and  future  equipment and in  future  applications.   This
report examines the replacement of R22 from two points of view:
 —  The feasibility of a-drop-in replacement  for residential heat
     pumps,  air-conditioners  and window  air-conditioners  is
     investigated.
 —  Replacement  of  R22  by  refrigerant  mixtures  that  would
     potentially lead to energy savings by a completely  new design
     of the heating and cooling equipment.
                                10

-------
2.0  Simulation Approach

It is the goal of the theoretical analysis presented here to study

only the  effect of  the  thermodynamic properties of  the working

fluids.  The cycle model used resembles the ideal' vapor compression

cycle as closely as possible.  The only exceptions are a compressor

efficiency  of   0.7   and   the  use  of  air-to-refrigerant  heat

exchangers.   The latter  is necessary to ensure that  the gliding

temperature effect of mixtures is accounted fori,
                                               i

                                               I

2.1  Computer Model
                                               i
A computer model HAC1 was developed.  It is a UA-model in which the
                                               i
product of the overall heat transfer coefficient and heat exchange

area (UA) are given.   Prior  studies  have shown that a comparison
                                               i
between pure and mixed working fluids provides meaningful results

only when the fluids  perform identical task.  This implies that the
                                               !
air streams  being heated or cooled undergo the  same  temperature

changes at  the  same  flow  rates  independent of whether or  not a

mixture or pure component is used /4/.  This can be obtained in a

consistent way with a UA-model.  It is assumed that the temperature

glide of the mixtures is linear, though  this  is  not always true.

The implications of this assumption are discussed under Results and

Discussion.  HAC1 uses the  Newton-Raphson method to solve a set of

eight non-linear equations simultaneously.   To have the design of

the heat pump affect the results of the calculations to the least

possible degree, almost all operating  parameters were set to ideal
                                11

-------
conditions.  Input values are the evaporator air inlet and outlet
temperatures  and the air  flow  rate,  the  condenser air  inlet
temperature and  flow rate,  heat exchange areas and heat transfer
coefficients   (estimated  based  on  actual  equipment) .    Other
variables  such as  pressure drops,  superheat  and  subcooling at
evaporator and condenser  outlet,  and superheating of the suction
gas  in  the compressor are  set  to zero.   It is  assumed  that the
compressor  displacement  is always  sufficiently  large  to  pump
whatever volume flow rate the evaporator  provides.  The isentropic
efficiency is set to 0.7.   For both,  the evaporator and condenser,
the  overall  heat transfer  coefficients  are 0.1  kJ/m2K,  and the
areas are 4.0 and 5.0 m2 respectively.  The cooling load is assumed
to be a sensible load only.
     According  to  today's  design  criteria,  the  outdoor  heat
exchanger which is the condenser during air-conditioning operation
was chosen to be  the  larger heat exchanger since the amount of heat
rejected is larger than the cooling capacity.  The evaporator has
to be  small to  provide  a  cooling  surface  on a  temperature low
enough for dehumidification.  Area and heat transfer coefficients
are  calculated based on  actual  designs.  For most  of  the results
presented here, it is assumed that all heat exchangers are counter-
flow heat exchangers.  The impact  of  cross-flow heat exchangers is
investigated in  Chapter  4.5.   It is  further assumed  that during
desuperheating of the vapor  in the  condenser,  the  inside  tube
surface temperature  is below the saturation temperature of the
vapor.     Therefore,  the  heat  transfer   coefficient   in   the

                                12

-------
desuperheating region  is  assumed to be the samp  as  for the two-


phase  region.    The heat transfer  process is  governed  by the


difference  between  the  dew   point  temperature  and  the  air-


temperature.  Each run of HAC1  produces an output  file as shown in


Exhibit 3 for pure R22.  The  first  section of the output describes


the program features in short and lists  the air flow rates.


     The second section of the output file states all input values,


the specified refrigerant mixing coefficient, concentration  (mass


fraction),  the  ambient temperature  and temperatures of  the air
                                               I

streams  into  and out  of  the evaporator and into the condenser.


Further  compressor  efficiency,   pressure   drops,   super  heat,


subcooling,  additional  superheat,  and  overall  heat  transfer


coefficients are listed followed by the heat capacity (calculated


by multiplying mass flow rate with specific heat)  and the cooling


capacity.   The  end of  this  section  of the  output shows  heat


exchanger  areas,  adjustment  factors  (1.0  all  the time)  and the


number of  segments  into  which each heat exchanger  is divided in


order to account  for the non-linearity of the  temperature glide.


For this  investigation the  number of segments was set  to 1.0 to
                                -•        -  -     I   ' •

speed up the calculation procedure.            J


     In  the third section of the  sample  printout the calculated


thermodynamic properties at each state point throughout the cycle


are listed.                                     ,


     The  fourth  section states  all  other calculated  results:


compressor  work,  the amounts of heat exchanged;  COP,  refrigerant


mass flow rate, volumetric capacity, pressure ratio, and compressor




                                13


-------
displacement.  Other output values are not  of concern here.   Energy


   Exhibit 3;    Sample Printout of  Computer  Run with HAC1.


    NEWTON-RAPHSON METHOD IS USED TO SOLVE A SET OF NONLINEAR EQUATIONS.
    HTFs USED.IN COND.  AND EVAP. ARE BOTH AIR.
    A VOLUME FLOW RATE  OF HTF IN EVAP.(CFM): 400.00
    A VOLUME FLOW RATE  OF HTF IN COND.(CFM): 800.00
    COOLING LOAD IS FIXED BY SPECIFYING HTF TEMPS. IN EVAP.
    IN COND. SIDE, TEMP. OF HTF ENTERING COND. IS FIXED.
    TEMP. OF HTF LEAVING COND. VARIES.
    CONSTANT UAs ARE USED IN CON. AND EVAP.
    CONSTANT COMPRESSOR EFF.
                                             1.000 MASS FRAC.R22
************* GIVEN PARAMETERS *****************
REFRIGERANTS R22    AND R22   ;  F =  .0000;  X =
AMBIENT TEMP:  35.0 C
HX STREAM TEMPS:  SOURCE (IN, OUT):   26.0,   10.6 C
               SINK   (IN):    35.0 C
COMPRESSOR EFFICIENCY : .7000
IMPOSED PRESSURE DROPS:  COND =    .0 KPA; EVAP =
IMPOSED E SUPERHEAT, C SUBCOOLING, ASHC (C):    .0
UA (EVAP, COND):  400.0,  500.0 W/C
HEAT CAPACITY OF HTF (EVAP,COND):  227.8, 417.6 W/C
COOLING LOAD: 3514.9 WATTS
AREA EVAP, COND, FACTOR E, C, NSEGM :4.00000,5.00000,1.00000,1.00000

************* STATE PARAMETERS *****************
                                                 .0 KPA
                                                  .0
.0
STATE


T
HX STR
1 EVAP
2 COMP
3 COHP
4 COND
5 CONO
6 COND
7 EVAP
8 EVAP
9 LSHX
OUT
IN
DIS
VST
LST
OUT
IH
VST
OUT
26

45
44
35
35
10
26

.0
.0
.9
.0
.0
.0
.6
.0
.0
(C)
REF
6.6
6.6
87.1
51.5
51.5
51.5
6.6
6.6
51.5
P
(KPA)
613.6
613.6
2014.5
2014.5
2014.5
2014.5
613.6
613.6
2014.5
H
(KJ/KG)
253.4
253.4
296.3
263.4
109.1
109.1
109.1
253.4
109.1
V
(MA3/KG)
3.86E-2
3.86E-2
1.32E-2
1.13E-2
9.31E-4
9.31E-4
O.OOE+0
3.86E-2
9.31E-4
S
(KJ/KG K)
.000
.000
.000
.000
.000
.000
.000
.000
.000
XL
(MASS
1.000
.000
.000
.000
.000
.000
1.000
.000
.000
XV
FRAC)
1.000
.000
1.000
.000
.000
.000
1.000
.000
.000
XQ

.000
.000
.000
.000
.000
.000
.282
.000
.000
    ************** CALCULATED PARAMETERS **************
    WORK * 1043.5 QEVAP = 3514.8 QCOND = 4558.3 HX21 -    .0 HX67 =    .0 WATT
    COP  * 3.368  REF. MDOT=  .0243529 KG/S VCR= 3735. KJ/MA3  PR =  3.28
    VOLUME FLOW RATE (CC/SEC) :  941.12
    LHTD IN EVAP (GIVEN, CAD, LMTD IN COND   8.787    8.787  11.641
    AIR TEMP DROP, REF TEMP GLIDE IN EVAP   15.430    .000
    AIR TEMP GLIDE, REF TEMP DROP IN COND   10.915    .000
    COMPRESSOR DISPLACEMENT VOLUME =20.4592 CC/REV
    ENERGY BALANCED SUP.C SUB,SUP(FRAC HEAT):  .00   .04 800.52
    ENERGY BALANCED SUP.C SUB,SUP(UALMTD   ):  .00   .04 800.54
    EVAP SUPERHEAT, COND SUBCOOLING & SUPERHEAT: (C)   .00    .00  35.55
    FRACTIONS HEAT IH EVAP TP,SUP,COND SUB,TP,SUP:1.000 .000  .000 .824  .176
    FRACTIONS AREA IH EVAP TP,SUP,COND SUB,TP,SUP:1.000 .000  .000 .728  .272


balances  are  used to  verify thermodynamic consistency.   Other data


are   available   for   detailed   design   of  air-conditioners.     The


particular heat  pump design modelled  here  implies  that  the  four-


way-valve,  that  switches   from  heating  to  cooling,  maintains the


counter-flow characteristic  of the  heat  exchangers.    This  is not
                                            14

-------
true for conventional systems.  The air flow rates are 400 cfm for
the  indoor  heat  exchanger   (the  evaporator  during  the  air-
conditioning mode)  and 800 cfm for the  outdoor  heat exchanger.
These  values  are  specified   in  the   ASHRAE  Standard  for  the
respective heat exchangers for a cooling load of one refrigeration
ton.                                           !
2.2  Refrigerant Properties
The refrigerant properties are obtained based on the CSD equation
of state that was developed at NIST /5/.  The subroutine BDESC is
listed in  Appendix #1 which  shows  all coefficients of  the pure
refrigerants as they  are  used for this report.•  This facilitates
reruns which may become necessary as coefficients are updated.  For
mixtures the CSD equation of state requires a mixing coefficient.
For the work conducted here, the mixing coefficient is assumed to
be -0.01 for all mixtures.  This value is an avferage of the known
values and was used because no mixing coefficients were available
for the fluids under investigation.
2.3  Refrigerant Mixtures
The choice of substitutes was limited to fluids that are as similar
to R22 as possible to minimize  changes to current, equipment.   In
selecting the pure refrigerants  that can serve as constituents for
mixtures, priority was given to those  fluids  that do not contain
chlorine, with R124 as an exception because of its very low ozone
depletion potential.   Further, in order to limit the effect of the

                                15

-------
temperature glide to an acceptable range, the boiling point may not

be too  far from  that of R22.   The  following  refrigerants were

selected:  R143a, R32, R125,  R152a,  R134,  R134a  and R124.  At this

time no manufacturer plans to produce R134.

     Refrigerants  R143a, R32  and  R125  are  "low boilers" with

boiling points below that of R22, while refrigerants R152a, R134,

R134a and R124 are  "high boilers" with boiling points above those

of R22.  The binary mixtures investigated here consist of one low

boiler  and   one  high  boiler.     During   the  course  of  the

investigation, it became clear that mixtures containing R32  show a

consistently better performance than those with  other low boilers.

Results are presented for the following mixtures:

                         R32/R134a,
                         R32/R152a,
                         R32/R134,
                         R32/R124,
                         R143a/R134a,
                         R143a/R152a,
                         R143a/R124,
                         R125/R134a,
                         R125/R152a,
                         R125/R124.

Since R32, R152a and R143a are flammable components,  it was decided

to also investigate the  ternary mixtures:

                         R32/R152a/R134a,
                         R32/R152a/R134 and
                         R32/R152a/R124.

It  is  expected  that the  ternary  mixtures  can  substitute for

R32/R152a.   The addition of a nonflammable component will  reduce

the overall flamraability of the mixture.  However, extensive tests

are necessary to evaluate the flammability.

     Future  work will include the evaluation of ternary mixtures

                                16

-------
which contain small amounts of R22 increasing the likelihood that
             -            . ' '   '         • ""       ' i

existing lubricants can be used.





2.4  Operating Conditions


Typical  numbers   for   operating  conditions  are  derived  from


performance  data  of  existing  residential  air-conditioners  as


described in the ASHRAE testing and rating procedure /6/.


Air-conditioning:   Outdoor air inlet temperatvire      95 F


                    Outdoor air outlet temperature  floating


                    Indoor air inlet temperature       80 F


                    Indoor air outlet temperature      52 F

                                               j
                    (based on  the  specified  air flow rate of 400


                    cfm per ton of cooling)


These  temperatures  represent  the  design  point  of  the  air-


conditioner.  At the above  specified values, the air-conditioner

                             ,
meets the building  load at steady state operation.  For less severe


cooling cases the  thermostat cycles  the  equipment on and off.   A


second case  is  evaluated with  82  F outdoor temperature  and all
                                               i

other conditions are unchanged.   This value is usually measured


under part load  operation when the equipment is cycling on and off.


The part load performance can be reduced  by up to 25 % compared to


steady state operation.  However, when the air-conditioner has an

                                               ,
automatic  expansion valve   this  degradation,  caused  by  fluid
                                                               .

migration during the off-cycle, can be almost entirely eliminated


/7/.  It is assumed that the part-load performance is identical to
                                               I

the steady-state performance at  that condition for  the following



                                17

-------
reasons.  Cyclic losses have two major sources, the heat capacity
of the heat exchangers and of the working  fluid, and the migration
of the  refrigerant  during the off  periods.   Experimental results
show that  by eliminating the refrigerant migration,  the cyclic
losses are eliminated almost entirely, up to 90% /7/.  These losses
will  not effect  the  ranking  of  the  fluids  investigated  here
assuming  migration  can  be  eliminated.   Usually,  thermostatic
expansion valves,   which  represent  state-of-the-art  technology,
prevent  refrigerant  migration.    The  performance  of  the  air
conditioner is linearly interpolated between  the two rating points
                                                          »
allowing for the entire cooling temperature x-ange  to be covered.
     For heat pumping it is generally accepted design practice that
the air-conditioner designed for the cooling  application has to
serve as a heat pump as well, although the unit's capacity is not
optimized for this  application.  The simulation accounts for this
fact.   For heating  applications the function of the outdoor heat
exchanger and the indoor heat exchanger  are reversed.  Thus in the
model, the heat pump condenser is now described with the evaporator
air  flow rate and  UA  value and vice  versa.   Calculations  are
performed at two cases.   For both cases the indoor air conditions
are:
Heat Pumping:  Indoor air inlet temperature:       70 F
               Indoor air outlet temperature:  floating
and the first outdoor air case is:
               Outdoor air inlet temperature:     47 F
               Outdoor air outlet temperature:    33 F

                                18

-------
                (based on an air flow rate of 800  cfm)
 The second operating condition is  heat pump operation  at 17  F
 outdoor air inlet temperature.  Typically,  even  the  continuously
 operating heat pump does not reach the  full  capacity required by
 the building  and  resistance heat has to  be used to  supplement the
 heat pump.                                      i
       •
                                               . i
 2.5 Capacity Modulation with  Mixtures
                                               , i
 It  has  been repeatedly  reported and implemented  in at least one
 commercial  product  that  the  capacity  of  a heat  pump  can  be
 controlled, within certain limits by changing the  concentration of
 the circulating mixture  /8-11/.  With this  effect the capacity of
 the heat pump does not drop off as  rapidly as it would with a pure
 refrigerant.   In  turn,  the need for resistance heat (COP=l.O)  is
 reduced.   Since a  heat  pump has  a  COP  larger than  1.0  even  at
 severe operating conditions, energy savings can be accomplished by
 this maneuver.
     Since  the pressure controls the specific vapor  volume,  the
mixture concentration determines the mass flow rate of a compressor
with constant speed and  displacement volume is able to establish.
The range  of  pressure that can be covered  depends  on the device
that  accomplishes  the   concentration  shift,  the difference  in
boiling points of the constituents of the binary mixture,  and the
initial concentration.  For ternary mixtures the situation is more
complex and the range of pressures  depends on  the boiling point  of
the intermediate component as well.

                                19               !

-------
     The use of a mixture as  a substitute for R22 implies that the
concentration is  selected so that the vapor pressure is close or
equal to R22.   This entails that the capacity of  the mixture is
also similar to the capacity of R22.  These similarities mean the
compressor and motor size do not have to be modified.  However, by
changing the mixture concentration,  the vapor pressure changes and
the capacity can be modulated.
     The change in concentration can be achieved by passive means,
which do not require  any additional controls,  or by active means
such  as rectification  columns,  which usually require controls,
valves  and possibly additional, parasitic  power.    The range of
composition shift by passive means  is limited.
     The simplest way of affecting  a shift in concentration is to
use an  accumulator at the evaporator outlet.  This represents a
passive means.    Whenever  liquid   floods out  of  the  evaporator
because the  outdoor temperature is  dropping,  it  is stored in the
accumulator.   Since the liquid's concentration is different  from
the   overall   concentration  circulating  in   the   system,  a
concentration shift is accomplished.  A higher pressure mixture is
left  circulating.   The  accumulator  is  a passive device.   No
auxiliary  power,  valves or  other  controls  are required.   Its
capability to affect  the concentration is limited.
      The rectification  column used  in a Japanese  heat pump is  more
effective  in shifting  the  concentration /II/.   However, active
controls and valves are required. Other concepts  suggest molecular
sieves  as  a  separation  means /8/.
                                 20

-------
      The  use of a variable  speed  drive will accomplish the  same
 goal  of obtaining a variable capacity.  By combining variable speed
 and   shifting   concentration  the   available range  of  capacity
 modulation  is considerably  increased.
      The  effect of the  rectifier is modeled  here by repeating the
 calculation for the  low temperature heat pump case  using the  same
 mixture  with a different concentration.    It is  assumed  that a
 concentration change of 20 % is achievable with |a rectifier.   This
 is an arbitrary number,  but rectification processes far exceed  such
 a composition shift and a twenty percent change 'is achievable  with
 rather simple equipment.                       !
      Concentration shift requires that part of the charge is stored
 somewhere in the heat  pump.   The  system  has to be  designed to
 operate  independent of the  amount of charge,  and  the  charge
required  is  expected to be  larger than for  a
pump.
     In an experimental project it was  determined that a heat pump
operating on  a mixture of R13Bl/R152a that utilizes composition
shift  using just  an accumulator,  yielded an
increase over a heating season /10/.
3.0  Seasonal Performance Evaluation
The  seasonal  performance expressed  by the  seasonal  performance
factor (SPF)  is defined as the ratio of the total amount of cooling
provided during a season  divided by the total amount of electrical
energy consumed during  that season  for  the purpose  of  cooling.
conventional heat
11  % performance
                               21

-------
This  factor is very  similar to  the coefficient  of  performance
(COP) .  The only  difference is that the  COP  is an instantaneous
value of  a continuously operating air-conditioner while  the SPF
represents an average  over the entire season.  The heating seasonal
performance factor (HSPF) is defined in an analogous way: the total
amount  of heating supplied to a  building divided by  the total
amount of electrical energy consumed for heating purposes.  Total
electrical  energy  consumption refers  to  compressor  power  and
additional  electrical heaters required to meet the building load.
Fans  and   controls  are  not  included.    In  this  report  the
abbreviation CSPF refers to the cooling SPF, and HSPF refers to the
heating SPF.
      In  order to  determine the  SPF the  ASHRAE  Temperature Bin
Method is employed as outlined in the testing  and rating standards
for heat pumps /6/.  For the purpose of the bin  method the  outdoor
temperature scale  is  divided into temperature intervals or 'bins'
each  of a span of 5 F, for  example from 70 F to  75  F.  Each bin is
characterized by an average temperature.  For  example  the bin from
70 F to 75 F has an  average temperature  of 72  F.   It  is  assumed
that whenever an outdoor temperature is found in the range  from 70
F to  75 F that the equipment performs as if the temperature were 72
F for that time period.  It is necessary  to know how  many  hours  a
temperature is found in the respective bin during an entire season.
The number of hours varies with  the climate.  Exhibit 4 lists the
bin  temperatures  for  one  generalized  cooling climate  and six:
typical heating climates spanning the various  climate  zones in the

                                22

-------
                          Exhibit*
            Fractional Temperature Bin Hours for
         Six Heating Climates of the Continental US
Region
Heating Load Hours
Outd. Design T. (°F)
Bin*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Bin Temp.
62
57
. 52
47
42
37
32
27
22
17
12
7
2
-3
-8
-13
-18
-23
I
750
37
I
1250
27
III
1750
17
IV
2250
5
V
2750
1 -10
VI
2750*
30
Fractional Bin Hours
.291
.239
.194
.129
.081
.041
.019
.005
.001
0
0
0
0
0
0
0
0
0
.215
.189
.163
.143
.112
.088
.056
.024
.008
.002
0
0
0
0
0
0
0
0
.153
.142
.138
.137
.135
.118
.092
.047
.021
.009
.005
.002
.001
0
0
0
0
0
.132
.111
.103
.093
.100
.109
.126
.087
.055
.036
.026
.013
.006
.002
.001
0
0
0
.106
.092
.086
.076
.078
.087
.102
.094
.074
.055
.047
.038
.029
.018
.010
.005
.002
.001
.113
.206
.215
.204
.141
.076
.034
.008
.003
0
0
0
0
0
0
0
0
0
* In Pacific Coast Region

                         Exhibit 4a:
            Fractional Temperature Bin Hours fair
     a Generalized Cooling Climate of the Continental US
Bin*
1
2
3
4
5
6
7
8
Bin Temp.
67
72
77
82
87
92
97
102
Fractional Bin Hour
.214
.231
.216
.161
.104
.052
.018
.004
                              23


-------
US.  Exhibit 5 shows a map indicating the heating climates.

     In Exhibit 4 the total number of cooling  load hours  (CLH) and
heating load hours (HLH) are specified (that is the number .of hours
in  a  season during  which cooling  or heating are  required)  and
fractions of total load hours for each temperature bin.  The air-
conditioning performance is evaluated for one  standardized climate
where the total number of hours that require cooling capacity  (CLH)
is 3825 hours.
     For climates where heating is required, there are six typical
climate regions  distinguished by their  total heating  load hours
(HLH)  and the  heating load design temperature.  The first region
has a  total of  750 heating  load hours.   It represents  a  very
moderate climate  found  in Florida or southern Texas,  Exhibit 5.
The lowest temperature bin encountered is usually in the range of
22 F for about one hour during a typical season.   The most severe
climate region (Region V) is found in a belt  through the northern
states in the US  and  the total heating load hours  are given as 2750
hours.  The lowest temperature bin is at  -23 F.  A sixth  region is
introduced to  account  for the Pacific North  West.  The number of
cooling  load hours  is  very  high,  2750 hours,  even  though the
temperatures are very moderate, the lowest temperature bin is at 22
F just as in Region I, i.e. Florida.  With the help of the map in
Exhibit 5, it is possible to select for any location in the US the
                                              /
appropriate region and determine the seasonal heating performance
for a heat pump.

                                24

-------
    3
    O
    CO
    CO
   ts
    O
10
    O
   CO
   CO
                                 25

-------
26

-------
     In the evaluation of  the  HSPF,  resistance heat is included.
The resistance heat is treated  as an  additional power input to the
heat pump with a coefficient of performance (COP) of 1.0 whenever
the heating  capacity of the heat pump drops  below the building
requirement.  For the results presented here no poricentration shift
is considered which is discussed later in detail.  Exhibit 6 shows
a sample calculation.  The upper section pertains to cooling, the
lower to the  first of the six heating cases.  [ In the upper left
hand corner, the name of the refrigerant is lissted  (here R22/R22,
since this is the case of pure  R22).   In addition, the CLH of 3825
                                               i
hours and the cooling design temperature of 95  F are given.  Next,
the OOP's  are listed for  two  conditions,  95  F ctnd 82  F outdoor
temperatures respectively, and the design cooling capacity of 3.5
kW is given.   The first column lists the  bin
lists the characteristic bin temperature  in  F,
number, the second
 and the third the
temperature in K.   The fourth column gives  the  fraction of..tine
during which  a  temperature is  found  in the  respective  bin, the
fifth lists the cooling capacity, the sixth column shows the amount
of cooling provided for one hour and the seventh  cplumn the COP of
the air-conditioner for the respective temperature bin.  The COP is
linearly interpolated based on the  two  values
eighth column gives the power requirement  for the compressor.  The
ninth column lists the amount of electric energy consumed for one
hour  of  cooling  while  the  temperature  is   in  the  respective
temperature bin.  The over all results are listed in, the tenth
listed above.  The
                                27

-------
Exhibit 6; Sample  Seasonal Performance Calculation.
   FLUID R22/R22
   SEASONAL COOLING PERFORMANCE

SIN if
1
2
3
4
5
6
7
8
TOTAL ENERGY
BIN
F
67
72
77
82
87
92
97
102

TEMP CLH FRAC
K
292.6
295.4
298.2
300.9
303.7
306.5
309.3
312.0


0.214
0.231
0.216
0.161
0.104
0.052
0.018
0.004

CLH 3825
COP (95) 3.37
COP (82) 4.34
DESIGN CAPACITY 95
. CLOAD CLOAD
kW
0.233
0.817
1.400
1.983
2.567
3.150
3.733
4.317

kWh/h
0.050
0.189
0.302 •
0.319
0.267
0.164
0.067
0.017
1 .376
DESIGN T:
F (kW):
COP

5.46
5.09
4.71
4.34
3.97
3.59
3.22
2.85

95
3.5
POWER
kU
0.043
0.161
0.297
0.457
0.647
0.876
1.159
1.516


kWh/h
0.009
0.037
0.064
0.074
0.067
0.046
0.021
0.006
0.324







kWhel
1238.
CkWh
5261 .


















CSPF
4.25


SEASONAL HEATING PERFORMANCE












HLH
COP (47)
COP (17)
750
3.67
2.57
DESIGN CAPACITY 35

BIN #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
TOTAL ENERGY
BIN
F
62
57
52
47
42
37
32
27
22
17
12
7
2
-3
-8
•13
-18
-23

TEMP HLH FRAC
K
289.8
287.0
284.3
281.5
278.7
275.9
273.2
270.4
267.6
264.8
262.0
259.3
256.5
253.7
250.9
248.2
245.4
242.6


0.291
0.239
0.194
0.129
0.081
0.041
0.019
0.005
0.001
0
0
0
0
0
0
0
0
0

. HLOAD
kW
0.350
0.933
1.517
2.100
2.683
3.267
3.850
4.433
5.017
5.600
6.183
6.767
7.350
7.933
8.517
9.100
9.683
10.267

HLOAD
kUh/h
0.102
0.223
0.294
0.271
0.217
0.134
0.073
0.022
0.005
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.342
DESIGN T:


F (kW):
COP

4.22
4.04
3.85
3.67
3.49
3.30
3.12
2.94
2.75
2.57
2.39
2.20
2.02
1.84
1.65
1.47
1.29
1.10

37
47

3.5
POWER
kw
0.083 .
0.231
0.394
0.572
0.770
0.989
1.234
1.510
1.822
2.179
2.591
3.071
3.639
4.319
5.151
6.190
7.526
9.305





kWhel
284.
HkWh
1006.




HSPF
3.55


RESISTANCE
kWh/h
0.024
0.055
0.076
0.074
0.062
0.041
0.023
0.008
0.002
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.365







0.
0.
1,
2.
2.
3.
3.
4.
5.
5.
6.
6.

kU
0
0
0
0
0
0
35
93
52
10
68
27
85
43
02
60
18
77

kUh/h
0
0
0
0
0
0
0.006 "
0.005
0.002
0
0
0
0
0
0
0
0
0
0.013
column as  total electric energy consumed for the season in kWhel
and total  amount of cooling provided in kWhc.  The ratio of these
two numbers yields the CSPF of 4.25.
     The lower  section of Exhibit  6  refers to the same calculation
for the first heating case.   In this case the lowest temperature
bin for which  heating is  required  is  22 F.   The  meaning of  the
first nine columns  is the same as  for the  upper  section of  the
                                 28

-------
table, with the term  'cooling1  replaced by 'heating1.   The tenth

and eleventh columns show the power requirement and consumption of

electric energy due to the resistance heat.  Zeros in the eleventh

column indicate that no resistance heat is needed because the heat

pump  capacity  is  sufficient (for high  bin temperatures)  or no

heating is required at all  (below a bin temperature of 22 F in this

case).

     All seasonal performance calculations were performed according

to this method for the fluids listed in the Chapter 4.2.
     •

4.0  Results and Discussions                  i

4.1  Performance Under Design Conditions

A total  of 500 runs  were conducted  with  HAC1 to  determine the

performance of the pure components and  their mixtures  listed in
                                              i       •     •
Chapter  2.3.   An  additional  190 runs  were  conducted with the
                                                ,
ternary  version,  HACT1,  for the  three ternary  mixtures.    The

results  for  all  runs  are available  in  data files that  contain
                                              i
complete printouts as shown in Exhibit 3.  Each run also generates

a short output file that contains the most crucial results.  The

short output files  for all runs are listed in Appendix 2 with a

list  of  code numbers  for  the  refrigerants.    The  following

parameters  are listed  in  the short  output  files:  fluid code

numbers, Rl, R2;  mixing coefficient,  FO;  concentration,  x  (mass

fraction);  COP;  volumetric  capacity,  VCR;  pressure ratio,  PR;
                                              I
suction pressure,  Ps;  discharge pressure, Pd; cooling load, CLOAD;

compressor work,  WORK; the compressor discharge;temperature,  Tsup;

                                29

-------
and the evaporator air inlet temperature in C, Tairin.  The first
set lists all mixture runs  at  design  conditions.   The second set
lists  those  runs  that  were  used   for  seasonal  performance
calculations.  It contains R22 values for comparison.
     In this chapter the results are discussed that were obtained
for the design conditions at 95 F outdoor air temperature for air
conditioning and 47 F outdoor air temperature for heating.
     Exhibits 7 through 9  show  the COP and volumetric capacity for
the cooling  cases  of  the binary mixtures listed  in Chapter 2.3.
R22 has a cooling COP 3.37 and a volumetric capacity of 3735  kJ/m3.
In this  simulation, the heating COP is calculated  for a cooling
case under heating conditions.   Therefore, in order to obtain the
true heating COP  the  values  shown  in the  Appendix have  to  be
increased by  1.0.   This was considered in  the  evaluation of the
seasonal performance.   Based on the peak performance for cooling,
the mixture  concentration  is selected that will  be used for the
investigation of the  seasonal  performance.    A  comparison of the
concentrations at which optimum performance is achieved for cooling
and those at which the heating performance is optimum yields that
there are only minor differences of  less than  0.1.  Therefore, the
                                30

-------
            it  7:     Cooling  COP  and  Volumetric  Capacity  for  Binary
    Refrigerant Mixtures.
      COP
      4 .
    2.5
VCRfBtu/ff3)
    180 —
    160

    140

    120



                     0.2
0.4           0.6

Concentration ofR-32
            R-32/R-134   -*-  S-32/R-134a   -*- R-32/R-124   -a

                                        31              I
                            R-32/R-152a

-------
     Exhibit 8;	Cooling  COP  and  Volumetric  Capacity for Binary
  Refrigerant Mixtures.
VCRfBtu/fi3)
    180
     20
                               0.4          0.6

                           Concentration of R-143a
           R-143a/R-134a
R-1433/R-124


      32
R-143a/R-152ai

-------
   Exhibit  9;      Cdolinor  COP  and  Volumetric  capacity  for  Binary
 Refrigerant: Mixtures.

VCR(Btu/fT

   180
                   0.2
    0.4

Concentration ofR-125
            R-125/R-1343
      R-125/R-124


            33
•-  R-125/R-1S28

-------
same  concentration  can  be  used  for both  cases,  without  any
significant penalties in COP.
     As a  comparison of the Exhibits  7-9  shows,  the cooling COP
spans a rather wide range from 2.45 for R125 to a maximum of 3.83
for  the  mixture  of  R32/R152ci/R124  with  a  concentration  of
0.2/0.2/0.6.
The results obtained for binary and ternary mixtures are summarized
in Exhibits 10 and lOa.  R22 is listed first as reference.
Mixtures are listed in sequence according to their performance.
     The best mixture was found to be a ternary of R32/R152a/R124.
The COP is 13.7 % larger and the volumetric capacity 23 % smaller
than the respective values for R22.
     The mixture R32/R124 is the best binary fluid pair.  The COP
is 13.4 %  larger and the volumetric capacity 9.6  %  smaller than for
R22.  The ternary mixture of R32/R152a/R134 ranks  third and is the
best chlorine-free fluid, followed by the binary mixture R32/R152a
with 12.1 % improvement in COP and with a volumetric capacity that
is 2 % larger as that of R22.  R32/R152a provides essentially the
same capacity than R22 and could be used as a drop-in replacement.
The fifth ranked mixture is the binary R32/R134.  The sixth mixture
which is the last showing an improvement  in excess of 11 % in COP
over R22 is R32/R152a/R134a.  The best heating performance is found
for the same (or only  marginally different)  concentrations that
show maximum cooling performance.  Since the operating conditions
in heating  are  more severe,  i.e.  the  temperature lift is larger,
the increase in COP is less pronounced than for cooling.

                                34

-------
Exhibit  10;    GOP  of  Mixtures  in Sequence  According  to  Their

Performance.
                                               i

R22 is  listed  first as reference.   For ternaries  the  amount of
R152a   was  traded   for   amounts  of   the  third   component.
(concentration in mass fraction)                              ,
IR1

R22
R32
R32
R32
R32
R32
R32
R125
R32
R143a
R143a
R152a
R134
Rl34a
R32
R124
R143a
R12S
IR1

R22
R32
R32
R32
R32
R32
R32
R125
R32
RU3a
R143a
R152a
R134
R134a
R32
R124
R143a
R125
IR2 IR3

R22
R152a R124
R124
R152a R134
R152a
R134
R152a R134a
R152a
R134a
R124
R152a
R152a
R134
R134a
R32
R124
R143a
R125
IR2 IR3

R22
R152a R124
R124
R152a R134
R152a
R134
R152a R134a
R1S2a
R134a
R124
R152a
R152a
R134
R134a
R32
R124
R143a
R125
X1

1
0.2
0.3
0.3
0.4
0.3
0.4
0.2
0.3
0.3
0.1
1
1
1
1
1
1
1
X1

1
0.2
0.3
0.3
0.4
0.3
0.4
0.2
0.3
0.3
0.1
1
1
1
1
1
1
1
X2


0.2
0.7
0.4
0.6
0.7
0.5
0.8
0.7
0.7
0.9







X2


0.2
0.7
0.4
0.6
0.7
0.5
0.8
0.7
0.7
0.9







X3 COP

3
0.6 3
3
0.3 3
3
3
0.1 3

.37
.83
.82
.79
.78
.77
.76
3.58
3
3
3
3
3
3
3
3
2
2
.58
.57
.57
.56
.44
.33
.23
.04
.89
.45
X3 COP

3
0.6 3
3
0.3 3
3
3
0.1 3
3
3
3
3
3
3
3
.3
3
2
2

.37
.83
.82
.79
.78
.77
.76
.58
.58
.57
.57
.56
.44
.33
.23
.04
.89
.45
Change
%
0
13.7
13.4
12.6
12.1
11.8
11.7
6.2
6.2
5.9
5.9
5.8
2.0
-1.2
-4.2
-9.8
-14.3
-27.4
Change
«/
* j
0
13.7
13.4
12.6
12.1
11.8
11.7
6.2
6.2
5.9
5.9
5.8
2.0
-1.2
-4.2
-9.8
-14.3
-27.4
VCR
kJ/m3
3735
2878
3377
3439
3809
3512
3865
2511
3820
2170
2413
2308
, 1940
2342
6227
1382
3441
3305
VCR
BTU/ft3
100
77
91
,92
102
94
103
67
102
58
65
62
52
63
167
37
92
89
PR

3.3
3.4
3.3
3.4
3.3
3.4
3.3
3.6
3.4
3.5
3.6
3.7
3.84
3.72
3.35
3.94
3.11
3.31
PR

3.3
3.4
3.3
3.4
3.3
3.4
3.3
3.6
3.4
3.5
3.6
3.7
3.8
3.7
3.4
3.9
3.1
3.3
PSUC
kPa
614
412
495
493
551
512
563
372
589
339
353
332
287
369
1005
208
740
821
PSUC
psia
89
60
72
72
80
74
82
54
86
49
51
48
42
53
146
30
107
119
PDIS
kPa
2015
1409
1650
1672
1833
1740
1872
1324
1993
1175
1271
1219
1104
1373
3363
817
2301
2718
POIS
psia
292
204
240
243
266
252
272
192
289
171
184
177
160
199
488
119
334
394
Tsus
K
360
352
355
363
363
354
358
348
354
338
350
351
338
340
382
337
339
336
Tsup
r
189
174
180
194
194
177
185
167
177
149
171
173
148
152
227
147
151
146
                               35

-------
 fl)
 o
 CD
 Cft
 0)
00

"S
 O
00
              I

                    CM
                    CM
                    JP

                 I
               M
               I
             I
                                                                 03
&
CM

2
CO


DC
                                                                   CM
CO CO
                                                                 CM CM
                                                                 co in
                                                                        CM
        CM

       "i
                                                                        CO


                                                                        cc
                                                                        CM
                                                                       .LO
                 c

                 S
                 Q>
                 O)
                                                                        .812
                                                                                 o
cc
o
>

*
'o
                 E


                "5

                 0)
                JC
                c
                0)
                0)

                e>
                Q.
                                                                                 I
                                                                                 E
                                36

-------
      Of the pure fluids R152a ranks best with a 5.8 % improvement
 over R22,  followed by R134 with 2 % improvement and R134a with a 1
 % decrease.  These results indicate that R152a, R134 and R134a can
 be used as  replacement refrigerants,  achieving better or  about
 equal performance  as R22.    However,  the volumetric capacity  of
 these replacements is about 40 % smaller,  which requires the use of
 a 40 %  larger  compressor.                      I
                                               i
      In Appendix 2 all summary data  for all binary mixture runs are
 listed   in  English  units.    In   Appendix   3  results   for  the
 calculations with ternary refrigerant mixtures are presented  in
 English units.
      The best ternary mixture contains R124 with a concentration of
 0.6  indicating that the flammability  could be reduced compared  to
 the pure constituents, R32 and Rl52a.   For the other ternary fluids
 this  effect  is less pronounced.                                 •••;
      This analysis presents an idealized condition.  To what extent
 the  savings  found  in this  study  can  be  imp 1 eitier.ited will depend
 strongly on  the  actual  equipment  design and on secondary  effects
                                                                "V
 such  as the influence  of  pressure  drops,  superheating  of the
 refrigerant  in the  compressor, and superheating and subcooling  in
 the evaporator and  condenser.
4.2  Seasonal Performance
                                               I
The calculation of the seasonal performance was conducted for the
following fluids and mixtures:  the reference fluid R22, R32/Rl52a,
R32/R134, R32/R134a and  R32/R124.   The ternary mixtures are not

                                37              ; '       "   '

-------
included to shorten  calculation times.   It is  expected  that the
seasonal performance of the ternary mixtures will be quite similar
to the binary mixture of the same performance level.
     Since the  steady state performance under  design conditions
showed  clearly  that mixtures  containing  R32   are  the  primary
candidates for replacing R22, the seasonal performance evaluation
is limited to these mixtures.  The pure components were included to
demonstrate that the fluid  with the better performance under design
conditions shows also the  better seasonal performance.
     Exhibit  11 shows  a bar chart  of the  seasonal performance
factor  (SPF) for both heating and cooling seasons.  The first group
of bars represents the  cooling  seasonal performance  factor, CSPF,
and  the subsequent groups  represent  the  six climate regions for
heating.  A comparison  of  the fluids  indicates,  that when a  fluid
performs better in the cooling case it will usually  be better in
the  heating case.   Since  the  actual  performance  of any working
fluids  depends strongly on  the hardware  design, the ranking may
vary with  actual applications.   The   mixtures containing R32 show
significant improvements,  ' while  some of the pure fluids show  a
reduction  in the  SPF compared  to R22.  As  can be  expected from
previous discussions,  the  mixture  R32/Rl52a  exhibits  the best
seasonal performance,  followed by R32/R134  and R32/R134a,  while
pure R125  shows the poorest.  The last four lines in this table  are
explained in the section  'Concentration Shift1.
                                 38

-------
  0)
  o
      CO

     Z
      X

 §25
 o.S
 a>  ~o
 «  o

 CD  O
^^fc  ^^^^^
 CO

 O
 M
 CO
 CD
00
                   
                                &.
                                                                    £
                               a
                               CO

                               1
                                          co
             CM
                                    39
                                                                           
-------
Exhibit 12:  Seasonal Performance Factors  (SPF) for One Cooling and
Six Heating Climates.
The last four lines pertain to the influence of composition shift,
when a rectifier is  used.
      FLUID
             CSPF
                   HSPF I  HSPF II  HSPF III HSPF IV  HSPF V  HSPF VI
R22
R32/R124
R32/R134
R32/R152a
R1438/R124
R32/R134a
R125/R152a
R143a/R152a
R152a
R125/R124
R134a
R32/R152a
R32/R152a
R32/R124
R32/R124
4.25
4.84
4.79
4.77
4.59
4.57
4.5
4.47
4.45
4.45
4.23
4.77
4.84
4.84
3.949
3.55
3.94
3.86
3.88
3.67
3.71
3.7
3.7
3.7
3.62
3.48
3.82
3.62
3.94
3.908
3.13
3.44
3.38
3.39
3.21
3.25
3.24
3.25
3.25
3.15
3.06
3.34
3.21
3.44
3.629
2.7
2.94
2'.9
2.91
2.75
2.79
2,8
2.8
2.8
2.7
2.64
2.87
2.79
2.94
3.209
2.06
2.2
2.17
2.19
2.07
2.11
2.12
2.12
2.12
2.03
2.01
2.16
2.13
2.2
2.439
1.58
1.67
1.65
1.66
1.56
1.6
1.61
1.62
1.62
1.52
1.53
1.65
1.65
1.67
1.807
3.24
3.78
3.71
3.73
3.52
3.56
3.56
3.56
3.56
3.47
3.35
3.67
3.5
3.78
3.801
4.3  Concentration  Shift
In order to determine the suitability of the mixtures for capacity
control  by  concentration shift,  the  ratios  of  the maximum  to
minimum capacity are compared.  The numeric values  are  listed in
Exhibit 13.  The maximum and minimum values  are for the pure fluids
which  constitute a given mixture.   Although  in reality  only a
fraction   of  this  ratio   can  be  accomplished   without  very
sophisticated controls, it  indicates  the suitability of  a given
mixture.   It can be seen from  Exhibit 13  that  R32/R124  has the
widest  range  of composition  shift,  a  capacity ratio of  5.2,
followed  by the  second best mixture,  R32/R134,  with a ratio of
3.60.   The best performing chlorine-free  binary  mixture ranks
fourth with a ratio of 2.95.
                                 40

-------
Exhibit 13;  Ratio of Heating Capacities.

The R22 value  is given  for reference purposes.   Ternary mixtures
are not  listed since  fluid separation  is  less efficient*   The
capacities are listed in kJ/m3.
Mixture
R22
R32/R152a
R32/R134
R32/R124
R32/R134a
R143a/R152a
R125/R152a
R125/R124
R143a/R134a
R125/R134a
Capacity
1st comp.
3050
5179
5179
5179
5179
3035
3007
3007
3035
3007
Capacity
2nd com.
3050
1755
1444
999
1811
1755
1755
999
1811
1811
Ratio
1
2
3
5
2
1
1
3
1
1
.00
.95
.60
.20
.87
.73
.71
.01
.68
.66
Assuming  that a  realistic  concentration shift  of  0.2 can  be

accomplished with rather simple means  (short distillation column),

the SPF was  evaluated for two mixtures,  R32/R152a  and R32/R124.
                                               I
The first represents an example for a medium range capacity ratios,

and the second exhibits  the  largest capacity ratio.   The results

are listed in the last four lines of both sections of Exhibit 12.
                                               i
Exhibit 14  shows a  bar  graph that reflects the influence  of a
                                               i

concentration  shift.    For   cooling  there  is   no  change  in
                                               i
concentration and performance,  assuming  the original concentration

is used.   For  heating  the  HSPF is  consistently  higher with a

concentration shift.   The  increase  in HSPF is as  high as ten

percent for R32/R124 and  as high as six percent for R32/R152a.  For
                                               i .-
severe conditions, climate regions  II through V the  mixture with

the lower COP but larger capacity shift,  R32/R124  has the better

performance  by  up  to  6 %.   This  is because none or  little

resistance heat is required with  the  higher  capacity fluid.   The

                               41

-------
strong  influence concentration  shift  can have  on the  seasonal
performance complicates the situation.
     Depending on the given climate region one mixture may perform
better than others.  The amount of resistance  heat that is required
depends strongly on the design point  of  the heat pump.   If the
current design  practice would be  changed  so that the  heat pump
application determines the  size  of the air-conditioner,  the need
for resistance heat  could be reduced or  eliminated/ influencing the
choice of the replacement mixture.
     Actual energy  savings  achieved  by employing  concentration
shifts depend strongly on the climate and on actual operating and
design conditions over an entire year.
     In  this  chapter,   concentration   shift is  assumed  to  be
initiated by active means.  However, concentration shift can also
be initiated by passive means and the mere fact that some parts of
a  heat pump  store  refrigerant.    This  concentration shift  may
influence the performance of the system and has to be considered in
the design.
                                42

-------
    3
    O
 V
 o
    re
 CO
 B
 O
 CO
 CO
 O
CO
^r
                               k2222222Z^:2^^
                                  Hi
                            y/////////y//^//////A
              Y///S
              Illl
     1
                           Y/ZsTyZsT,
               <£>
        in
t~—i	h
CO     CM     T-
                                                   Q.
                                                   CO
                                      CO
                                                        ?

                                                        CM
                                           CO
                                           £

                                           in
                                           T-
                                           cc
in
s
CM
9
EE

-------
4.4  Drop-in Application vs. New systems
Although the modelling results presented in this report demonstrate
the potential for significant energy savings, only the application
of the  substitutes in actual machinery  can  demonstrate the real
potential.    The  closer  the  machinery  approaches  the  model
assumptions the closer the predicted energy savings are achieved.
Variables such as transport properties and  oil  compatibility which
were not  considered  in the model because  they are  not known for
most  of  the  proposed  substitute  mixtures  may  significantly
influence the actually achievable energy savings.
     However, the  mixtures discussed here may be    near drop-in
substitutes requiring  only changes  in  the  expansion  device  to
adequately  accommodate the  substitute.    Without  changing heat
exchangers,  the performance  of some  of the  better  fluids most
likely  would be  similar  to that  of R22.   How closely  the R22
efficiency  is  met   depends  on  the  selection  of  a  suitable
concentration,  which  primarily determines  the  capacity  of the
substitute and on  the degree to what the existing heat exchangers
approach  counter-flow characteristics.  It  is expected that the
performance of drop-in fluids for conventional  designs  is not very
sensitive  to  the   concentration   selected.     Therefore,  the
concentration would be chosen to match the capacity requirements,
at least  for  initial  tests.
     Based'on the simulation results, no reliable assessment can be
made  of  the performance  of  drop-in substitutes.    The actual
performance  can  only be  determined by  tests in  existing air-

                                44

-------
conditioners.

4.5  Implications of Counter-flow Design and the Use of Mixtures
A system designer developing  a  new system for operation with R22
substitutes should employ counter-flow heat exchangers,  or at least
those which resemble counter-flow as closely as possible, to take
advantage  of  the  gliding temperatures.    Conventional  design
practice relies on  cross-flow heat exchangers.   This is the best
choice  considering  the refrigerant saturation  temperature  is
essentially constant  and the  pressure drop on  the  air side very
small.  The fan power requirement is also small.
     In  this  study,  it  was  assumed  that  counter-flow  heat
exchangers are available, and that the temperature-enthalpy curve
in the two-phase range of a refrigerant mixture is'linear (linear
temperature profile). This is not always true.   Any deviation from
a  linear temperature  profile  reduces  the  performance to  some
degree.  To  investigate the penalty that  cross-flow heat exchangers
inflict on refrigerant mixtures, the model was updated to include
cross-flow heat exchangers.   The NTU method was  implemented for
counter- and cross-flow  heat exchangers.  For R22 the result is the
same for both heat  exchangers as  expected.   The mixture R32/R124
was chosen as an example since this fluid mixture has the largest
temperature  glide.     With   counter-flow  heat  exchangers  the
improvement over R22 for R32/R124 is 13.4 % as shown  in Exhibit 10.
With cross-flow heat exchangers the improvement over  R22 is reduced
to 8 %.  This result indicates,  in  order to take full advantage of

                                45

-------
the  performance   increase   mixtures   offer,   counter-flow  heat
exchangers should  be used.   This  finding has to be  verified by
experiments with refrigerant-to-air heat exchangers.
     When more  than four tube banks  are necessary in  order to
approximate counter-flow, the  pressure drop  on the  air side will
increase, leading  to higher fan power  requirements.   The energy
savings  mixtures  offer  may therefore be  offset  by  additional
parasitic losses.
     On  the  other  hand,   in  order  to  take  advantage of  the
refrigerant temperature  glide,  the heat  exchanger  area  could be
increased and the air flow rate could be reduced.  Thus the net fan
power may not change as  a result.   This would lead  to higher air
temperatures  leaving the  condenser,   a  feature  that should be
advantageous for heat pump applications.
     The use of mixtures would complicate the maintenance of heat
pump  systems.    One component may  escape preferentially  when a
leakage occurs.  The development of devices that allow the simple
determination of  the concentration of  the  remaining refrigerant
charge and of the  amount of the  components  that have to be added
can  eliminate this  difficulty.    Another solution could  be to
replace  the  entire charge,  which is practical only  when  the
original charge can be reclaimed and recycled.
4.6  Sensitivity Considerations and Accuracy
The accuracy of the results depends to a  large degree on the model
itself.  The model describes a heat pump  or air-conditioner almost

                                46

-------
as an ideal refrigeration cycle.  The only deviations from an ideal


cycle are the compressor efficiency  of  0.70  and the use of fixed


air temperatures instead of  fixed  saturation temperatures of the
                                                i

refrigerant.  The  latter choice  was  necessary to account for the


gliding temperature range of mixtures.   As has been shown, another


choice may  either  favor the  pure  component or  the mixture /4/.


Whether or not an actual design achieves the predicted performance


depends  largely  on the  system designer and  to what  degree the


idealized assumption can be met.  The closure on  the energy balance


in this model is  better than 0.1 %.  The  model applied here assumes


that the temperature glide is linear in the two-phase range.  For


most mixtures this  is not true.   Taking  into consideration any non


linearities will increase the calculation effort considerably but


could potentially change the ranking of the mixtures  of Exhibit 10.


This is true especially when comparing binary and ternary mixtures.


     However, there are  other  factors to consider. The accuracy of


the refrigerant data is one.  The work presented here is based on


the CSD  equation of  state as  published  and  provided by NIST /3/.


The version  used here is current, but  the  data for some  of the


replacement  refrigerants could  be  updated  in  ;the  future.   Any


update on refrigerant properties will effect the results reported


here to  an undetermined  degree which depends  on the magnitude of

                                                I
the changes.


     Another  uncertainty  results  from  the  use  of  a  mixing


coefficient of -0.01.  The mixing coefficient effects the results


to some  extent.    An as yet  unpublished  study  conducted  at EPA




                               47

-------
suggests  that  for mixtures  with  boiling points  in close proximity
of  one another,  as is the  case  here,  a  deviation in COP of less
than  3% can  be expected /ll/.  This  could  also  affect the ranking
of  the mixtures  in this report.
      The  analysis of the  seasonal performance  is accurate within
the accuracy of the bin method employed.  Generally  the bin method
is  suitable for  providing  overview  information  and is  used in
connection with the rating of air-conditioners and heat pumps.  The
model employed here uses the same information and reasoning as will
be  used later  for actual  testing of equipment.   Therefore,  it is
ensured that this  method  and actual tests  correspond.
4.7  Global Warming Potential  (GWP) and Ozone Depletion Potential
(ODP)
Exhibit 15 shows the effects of using pure and mixed refrigerants
on direct  global warming, indirect global  warming,  total global
warming and ozone depletion.  The value for the GWP of R32 is based
on a lifetime  estimate  from  EPA /3/.   The GWP and ODP values are
calculated by linearly interpolating between the pure components of
a mixture  and weighted with the  specific  volume of  the  liquid
leaving the condenser as compared  to these values  of R22.  In this
way the GWP and ODP is evaluated based on  the/ actual'charge within
a  system  (columns entitled  "Charge  Based").    The  underlying
assumption is made that  a  system charged with any fluid to the same
liquid level as  a system would be charged with R22  is optimally
charged.  The  values for  the pure substances  are  taken from /!/.

                               48

-------
The GWP is based on the integrated time horizon based on 100 years.


     The direct and  indirect  contribution to global warming were


calculated  based on the  seasonal  performance  factor  for  the


substitute  mixtures  based  on  a  refrigerant; charge  that  is


equivalent to seven  pounds of  R22  for the life time of ten years


for a heat pump.   It is assumed that 1.61b  of carbon dioxide is


generated per kWh of electricity.  The results for the direct and


the indirect contributions are shown in the  remaining columns of


Exhibit 15.  Exhibit  16 shows a bar chart displaying the direct and


indirect contributions.   The results show clearly that the proposed


substitutes  show less . impact on  the  global  wanning than R22.
                                                i

R32/R152a and R32/R124 have the lowest GWP.   The  first because the


contribution  of the  fluids  is  low,  the  second because  of  the


calculated  COP is  high.   Only  tests  in  actxial  machinery  can
                                                I
demonstate which of the  fluids will have the least•global warming


impact.
Depletion
FLUID

R22
R32
R152A
R134
R134A
R143A
R125
R124
R32/R152A
R32/R124
R32/R134A
R143A/R124
R125/R124
Potential.
I '
CONC.

1
1
1
1
1
1
1
1
0.4
0.6
0.7
0.3
0.3
VOL.
m3/kg
0.000907
0.00115
0.00119
0.000834
0.000887
0.0012
0.000693
0.000771
0.00118
0.00104
0.00109
0.000882
0.000795
GWP

1500
560
140
1200
1200
2900
2500
430
308
508
752
1171
1051
OOP

0.05
0
0
0
0
0
0
0.02
0.000
0.008
0.000
0.014
0.014
GWP
CHARGE
1500
442
107
1305
1227
2192
3272
506
237
443
626
1204
1199
OOP
BASED
0.050
0.000
0.000
0.000
0.000
0.000
0.000
0.024
0.000
0.007
0.000
0.014
0.016
GWP
TOT. CHAR
4755
1400
338
4137
3890
6948
10372
1604
750
1404
1984
3817
3801
SPF
cooling
4.25







4.77
4.84
4.57
4.59
4.45
Iridir.
GUP
72000

i
i
i



64.151
62(223
66958
66667
6»764
Total
GWP
76755







64901
64628
68942
70484
72565
                                49

-------
    cu

   "re
   JD
   CD
   S
    CO
 ..  o
to .Z
•CS  IM
   o
   13
    CO
                                                   *-   o
1
                                                               QL

                                                               O
                                                               ts
                                                               Q>
  I
                                                               CL
   £
   5

-------
     Of the  pure fluids considered  here,  R125 and R143a  show a
higher GWP than  R22,  Exhibit  15.   The only refrigerant with some
OOP is R124  with a value of 40 % of  that  of R22.   However, when
                                               j
these components are used as part of a mixture their contribution
is diminished.   The mixture with  the lowest GWP 237 is R32/R152a
with an OOP of 0.0, followed by R32/R124 with a GWP of 443 and an
OOP of  0.007.   Among  the  ternary mixtures, it  is  expected that
those with the  smaller additive of R124,  R134  or  R134a show the
smaller environmental  impact.   It  is concluded that  the binary
mixture  of  R32/R152a  is  the  most  favorable  fluid  from  an
environmental point of view with  regard  to all aspects, GWP, OOP
and potential for energy savings.   While the addition of a third,
nonflammable  component  reduces  the  risk  of  flammability,  it
increases the GWP and OOP.   Again there seems  to  be  a trade-off
between global risks  as  described by GWP and OI)P and  local risks
caused by the flammability of the fluids.
                                        "
5.0  Flammability and Materials Compatibility  |
5.1  Flammability
Out of the seven  refrigerants used in this investigation, three are
flammable: R32,  R143a  and R152a.    Phone calls to  refrigerant
manufacturers  produced  no   further  conclusive  and  referable
information.
     It is expected that R32 has the  lowest heat of combustion and
the lowest flammability of the three components.  It presents the
least  danger.    R152a  shows   the   highest flammability.    The

                                51


-------
concentration  ranges  for  combustible refrigerant-air mixtures are
12.7 - 33.4 vol% for R32, 4 -17 vol% for R152a and 7-18 vol% for
R143a.  With regard to mixtures there seems to be general agreement
that mixing flammable  with  non-flammable refrigerants reduces the
flammability.     However,  we  were   unable  to  ascertain  the
flammability limits of the  mixtures.

5.2  Materials Compatibility
Inquiries to refrigerant manufacturers yielded reluctance on their
behalf to  the release of  information  on  refrigerant- materials
compatibility.  The use of the ARI data base was recommended.  The
data base contains currently eighty reports  from various sources,
mostly manufacturers.  Since the. data base is not computerized yet,
a list of  titles was  obtained with  the following information of
concern  here:    There  are  13  reports concerning R134a,  2  for
R22/R142b, 2 for R124,  and 1 for R125.  None were available for any
other fluid investigated  in this report.   All reports that were
screened are listed below.   The  data  available and reported are
very scattered.  There is  no complete set of  information available
for a single refrigerant  nor  the information concerning the same
material for all  refrigerants.  .Taking this in to consideration, it
is not possible  to  generate a  general  table or chart.   This is a
clear indication that  further research  in this area is heeded.

Allled_Signal  Incorporated
     R.H.P. Thomas  and H.T. Pham, Evaluation of Environmentally
     Acceptable Refrigerant/Lubricant Mixtures for
     Refrigeration and Air Conditioning (R134a)
                               52

-------
     Refrigerant Breakdown Voltage for Isotron 22/142b Blends for
     Refrigeration:  Material Compatibility
Pennwalt Corporation

     Isotron 22/142b Blends for Refrigeration:
     Compatibility

Carrier Corporation
Material
     Solubility of R-123 and R134a in Oils
     Motor Materials in R-123 and R-134a
     UL 984 Tests with R-134a and Oils
     Polymer and Elastomer Performance in R-123 arid R-134a
     Sealed-Tube Texts of R-123 and R-134a with Mineral Oils
     Sealed-Tube Tests of R-12 and R-134a with PAGS

Copeland Corporation                           |

     Evaluation of Polyalkylehe Glycol Candidates with HFC-134a in
     Refrigeration Compressors  .
                  •.           •                  |

E.I. Dupont de Nemours and Company. Incorporated

     Compatibility of Elastomers with HFC-134a at About 25°
     Solubility of Refrigerants in Lubricants; HFC-134a

     Compatibility of HFC-134a with Refrigeration System
     Materials                                 :

     Compatibility of Alternative Refrigerants with
     Elastomers (R124)

     Mutual Solubilities of Water with Fluorocarbons and
     Fluorocarbon-hydrate Formation (R124, R15, R134a)

     Disassembly and Inspection of Compressor in
     Laboratory Refrigerator Charged with R-134a

ICI Chemicals and Polymers Limited

     Compatibility of Nonmetallic Materials with
     Refrigerants and Lubricants

Tecumseh Products Company
                                               i   '
     Materials Compatibility of R-134a in Refrigerant
     Systems                                    . .
                                               I
                                             .  I- .
                                53

-------
6,0  Further Work
To implement a fluid mixture proposed in this report, a number of
parameters have  to  be  considered and investigated.   They include
material  compatibility,  flammability  and  toxicity  as well  as
thermodynamic  and   transport   properties,   oil  compatibility,
compressor life,  and cost.  In addition, the actual performance of
the fluids and mixtures in air-conditioning and heat pump units has
to be verified by experiment.   This  includes the complete redesign
of systems. Lastly, concentration shift using  rectifiers (or other
means) has to be investigated.   Parallel  to this effort computer
simulation programs  have to be  extended  to account  for the non
linearity of the temperature glide.
                               54

-------
                           References

1.   Draft report of the United States Intergovernmental Panel on
     CFC emissions.   (This  reference will be updated  as soon as
     more detailed information is available.)

2.   Draft of the Revision to the Clean Air Act,.

3.   William Kopko,    Private Communication,  U.S. Environmental
     Protection Agency, Global  Change  Division, Washington D.C.,
     March 1991.

4.   McLinden, Mark O.  and R. Radermacher, Methods of Comparing the
     Performance   of   Pure   and  Mixed   Refrigerants   in  Vapor
     Compression Cycles, International Journal of Refrigeration,
     10, 6, 318-    325, (1987).

5.   Application of a Hard Sphere Equation of Sta.te to Refrigerants
     and Refrigerant Mixtures,   G.  Morrison, M,,O. McLinden,  NBS
     Technical Note 1226 (1988).                ;

6.   ANSI/ASHRAE Standard 116  (1983).

7.   Laboratory Investigation of Refrigerant Migration  in a Split
     Unit Air-conditioner, W. Mulroy,  D.A. Didion,, NBSIR 83-2756,
     (1983).

8.   Bedeutung  der nicht azeotropen Zwei-Stoff-Kaeltemittel  beim
     Einsatz  Waermepumpen und Kalteanlagen,  H. Kruse,  R. Jakobs,
     Ki Klima und  Kaelte Ingenieur,  8, 564-571,  (1977).

9.   The  Use of NARMs and Their Display in Ln(p)-h Diagrams, H.
     Schwind, Kaeltetechnik,  14, 98-103,  (1962).

10.  Performance of a Conventional Residential Heat Pump Operating
     With Nonazeotropic  Refrigerant  Mixtures,  W.  Mulroy,  D.A.
     Didion,  NBSIR 86-3422,  (1986).

11.  Development of Rectifying Circuit With Mixed Refrigerants, Y.
     Yoshida, S.  Suzuki, Y.  Mukai,  K. Nakatani and K.  Fujiwara,
     International Journal  of Refrigeration, 12,  182-187,  (1989).
                                                i
12.  Thermal Environmental Engineering,  J.L.  Threlkeld,   Second
     Edition, Prentice-Hall Inc. Englewood Cliffs, NJ,  (1970).

13.  Cynthia Gage,  Private  Communication,  U»S.  EPA, Research
     Triangle Park,  NC,  June 1990.              j

14.  Oak Ridge National Laboratory,  Private Communication.
                                55

-------
                                                  APPENDIX #1
 The following  pages of this  appendix  list the Subroutine BDESC  which  contains all parameters  for  the CSO
 equation of state that .were used to evaluate the properties of the pure refrigerants.
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C
 C

 C
 C
 C
 C
 C
 C
C
C
C
C
C
C
C
    BLOCK DATA BDESC

  THIS ROUTINE INITIALIZES THE COMMON BLOCKS CONTAINING INFORMATION
  ABOUT THE PURE COMPONENTS.  IT IS NOT REFERENCED DIRECTLY BY ANY
  OTHER SUBROUTINE BUT MUST BE INCLUDED IN THE EXECUTABLE ELEMENT.
  DATA ARRAYS ARE DIMENSIONED TO ACCOMODATE ADDITIONAL
  PURE COMPONENTS.

  EXPLANATION OF CONSTANTS:
     COEFF(I,J) - FOR REFRIGERANT J, COEFFICIENTS OF A,  B,  CPO
        CURVE FITS:
        A » AO * EXP(A1*T + A2*T*T)  (ICJ M**3/KMOL**2)
        B » BO + B1*T + B2*T*T  (M**3/KMOL)
        CPO a CO + C1*T + C2*T*T (KJ/KMOL K)
        (STORED IN ORDER AO,A1,A2,BO,B1,B2,CO,C1,C2>
     CRITU.J) - FOLLOWING INFORMATION FOR REFRIGERANT J:
        1=1- MOLECULAR WEIGHT
            2 - REFERENCE TEMPERATURE FOR ENTHALPY AND ENTROPY (K)
            3 - CRITICAL TEMPERATURE (K)
            4 - CRITICAL PRESSURE (KPA)
            5 - CRITICAL VOLUME  (M**3/KMOL)
     HREF(J) - REFRIGERANT NAME  (ASHRAE DESIGNATION)
     HZERO(J) - VALUE OF SATURATED  LIQUID ENTHALPY OF REFRIGERANT
        J AT ITS REFERENCE TEMPERATURE (KJ/KMOL)
     SZERO(J) - VALUE OF SATURATED  LIQUID ENTROPY AT REFERENCE
        TEMPERATURE (KJ/KMOL K)
     R - GAS CONSTANT (KJ/KMOL K)
     TOLR - RELATIVE CONVERGENCE  TOLERANCE FOR  ITERATION LOOPS
       SHOULD BE AT LEAST 10 TIMES  LARGER THAN  MACHINE PRECISION
     ITHAX - MAXIMUM ITERATION COUNT FOR ITERATIVE LOOPS
     LUP - LOGICAL UNIT TO WHICH ANY WARNING MESSAGES ARE WRITTEN
C
C
C
 A, B COEFFFICIENTS EVALUATED  FROM ASHRAE  (1981) SATURATION
 DATA UNLESS  INDICATED.

    IMPLICIT REAL  (A-H.O-Z)
    DIMENSION  COEFF(9,20),CRIT(5,20),HZERO(20),SZERO(20)
    CHARACTER*6 HREF(ZO)
    COMMON /ESDATA/ COEFF.CRIT
    COMMON /HREF1/ HREF
    COMMON /HSZERO/ HZERO.SZERO
    COMMON /RDATA4/ R
    COMMON /TOL/ TOLR,ITMAX,LUP
    COMMON /TOLSH/ TOLH.TOLS
   DATA R /8.314/
   DATA TOLR /1.0E-7/
   DATA TOLH.TOLS /0.01,0.00V
   DATA ITMAX,LUP /20,6/

 DATA FOR R11, R12, R13, R13B1, R14, R22, R23, R113, R114,
 R142B, R152A, R261A, R123, R143A, ISOBUTANE, R125, R134
 R134A, R32, METHANE

 R11, TRICHLOROFLUOROMETHANE

   DATA HREF(1) /'R11'/
   DATA (CRIT(I,1),I=1,5) /137.37EO,233.15EO,471.2EO,4467.EO,.247EO/
   DATA HZERO(1),SZERO(1) /Q.0,0.0/
   DATA (COEFF(I,1),1=1,9) /5394.655EO,-2.709516E-3,1.168022E-7,
  1  .1869326EO,-2.318627E-4,4.275137E-8,
  1  23.48052EO,.2510723EO,-2.28722E-4/

R12, DICHLORODIFLUOROMETHANE

-------
      DATA HREF(2> /'R121/
      DATA ,I=1,5> 786.47,233.15,369.3,5054.,0.1697
      DATA HZERO(6),SZERO(6> /0.0,0.0/
      DATA 
-------
c
c
c
   DATA HREFC10)  /'R142B1/
   DATA (CRITCI,10),I=1,5)  7100.49,233.15,410.3,4130.,0.2317
   DATA HZERO(10),SZERO(10) 70.0,0.07
   DATA (COEFF(I,10),I=1,9) /4512.576EO,-3.229507E-3,2.608976E-7,
  1  0.1730507EO,-2.648172E-4,  1.032608E-7,
  1  16.39145EO,.2717191EO,-1.589334E-47

R152A,  1,1-DIFLUOROETHANE

   DATA HREF(11)  /'R152A1/
   DATA CCRITU,11),1=1,5)  766.05,233.15,386.7,4492.,0.1817
   DATA HZERO(11),SZERO<11) 70.0,0.07
   DATA (COEFFCI,11),1=1,9) /3106.312EO,-2.776653E-3,-6.258540E-7,
  1   .1283451EO,-.1726218E-3,2.790653E-8,
  1   22.28316EO,.1539874EO,-3.015434E-67

R115,  PENTAFLUOROMONOCHLOROETHANE, C2CLF5

   DATA HREFC12)  /'R1151/
   DATA (CRIT(I,12),I=1,5)  7154.465,233.15,353.05,3153.,0.2527
   DATA HZEROC12),SZERO(12) 70.0,0.07
   DATA (COEFFCI,12),I=1,9) 76177.259EO,-5.540229E-3,2.635930E-6,
  1   .2474781EO,-6.346145E-4,5.512517E-7,
  1   20.0246EO,.3765849EO,-2.703487E-47

R123,  1,1-DICHLORO-2,2,2-TRIFLUOROETHANE

   DATA HREFC13)  /'R1231/
   DATA (CRITCI,13),I=1,5)  7152.930,233.15,456.94,3674.,0.2787
   DATA HZEROC13),SZEROC13) 70.0,0.07
   DATA (COEFFCI,13),1=1,9) /5885.629EO,-2.2446861E-3,-1.Q342735E-6,
  1   .1957662EO,-1.6784282E-4,-9.9567402E-8,
  1   29.2604EO,.302994EO,-1.92907E-47

R143A,  1,1,1-TRIFLUOROETHANE

  DATA  HREFC14)  /'R143A'/
  DATA  (CRIT(I,14),I=1,5)  784.04,233.15,346.3,3758.,0.1947
  DATA  HZERO(14),SZERO(14) 70.0,0.07
  DATA  (COEFFCI,14),1=1,9) /3092.03,-3.42907E-3,1.49460E-7,
  1   0.137902,-1.96301E-4.1.78383E-8,
  1   14.0656,0.254765,-1.29865E-47

R124:   1-CHLORO-1,2,2,2-TETRAFLUOROETHANE (R124)

  DATA  HREFC15)  /'R1241/
  DATA  CCRITCI,15),I=1,5)  7136.475,233.15,395.65,3660.,0.2447
  DATA  HZEROC15),SZERO(15) 70.0,0.07
  DATA  CCOEFFCI,15),I=1,9) /4718.786EO,-2.847854E-3,-1.0857E-6,
  1   .1818017EO,-2.256066E-4,-3.890926E-8,
  1  30.97765EO,.2542056EO,-9.364136E-57

R125:  PENTAFLUOROETHANE

  DATA HREFC16) /'R1251/
  DATA  CCRIT(I,16),I=1,5) 7120.03,233.15,339.45,3630.6,0.2107
  DATA HZERO(16),SZERO(16) 70.0,0.07
  DATA  (COEFF(I,16),I=1,9) /2971.488EO,-2.111917E-3,-3.734385E-6,
  1   .1443116EO.-1.410596E-4.-1.969504E-7,
  1  22.65024EO,.2956679EO,-1.694896E-47

R134:  1,1,2,2-TETRAFLUOROETHANE

  DATA HREFO7) /'R134'/
  DATA (CRIT(I,17),I=1,5) 7102.034,233.15,392.1,4562.,0.1897
  DATA HZERO(17),SZERO(17) 70.0,0.07
  DATA (COEFFCI,17),1=1,9) /3689.1EO,-2.83434E-3.-1.22280E-6,
  1   .144618EO,-1.84369E-4,-.253676E-7,
  1  32.5208EO,.222819EO,-1.06829E-47

R134A  1,1,2,2-TETRAFLUOROETHANE

-------
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
  DATA HREF(18) /'R134A'/
  DATA (CR1TU,18)«I=1,5) /102.030.233.15,374.3.4067.,0.199/

  DATA HZERO(18).SZERO(18) /O.O.O.O/
  DATA (COEFFU, 18). 1=1.9) /3611.8EO,-2.89497£-3,-1.28106E-6,
 1  .144618EO.-1.84368E-4.-.253676E-7.
 1  19.6704E0..258433EO.-1.178714E-4/.


R32:  DIFLUOROMETHANE


  DATA HREFO9) /'R32'/
  DATA (CRITU,19),I=1,5) 752.024,233.15,351.55.5814.23. .121V
  DATA HZERO(19),SZERO(19) /O.O.O.O/
  DATA (COEFFU, 19), 1=1,9) /1463.431.-1.212964E-3.-3.811882E-6,
 1  0.07560431,-5.783178E-5,-8.592812E-8,
 1  26.53804,0.05489753,1.574905E-5/


R141B


  DATA HREF{20) /'R141B1/
  DATA (CRIT /'I-PENT'/
  DATA (CRIT(I,14),I=1,5) /72.151,233.15,460.4,3384.255,0.305/
  DATA HZERO(14),SZERO(14) /O.O.O.O/
  DATA (COEFF(I,14),I=1,9) /4763.80,-6.8115E-4,-2.9477E-6,
  1  0.2131.-1.6519E-4.-1.3550E-7,

  1  0.0,O.O.O.O/


ISOBUTANE


    DATA HREF(15)  /'I-BUT'/
    DATA (CRIT /O.O.O.O/
    DATA  (COEFFU,20), 1=1,9) /623.650.-4.42548E-3.-2.66667E-6,

   1  0.0725603,-2.15762E-4.7.38690E-8,
   1  35.8200,-0.0340480,1.12485E-4/


 CHARACTERISTIC REFRIGERANT

-------
c
c
c
c
c
c
c
c
 DATA HREF{20> /'R-CHAR1/

 DATA  /100.0,50.,100.0,1000.0,0.07
 DATA H2ERO(20>,SZERO(20) /0.0,0.0/

 DATA (COEFF(I,20),I=1,9) /1064.,-0.01204,0.0,
1  0.1680,-8.066E-4,0.0,
1  44.40,0.5560,0.O/


 END

-------
                                 APPENDIX #2
This appendix contains a listing of the short output files for all computer runs conducted for binary mixtures.
The refrigerants are specified by code numbers according to the following table,.
                                 R22
                                 R142b
                                 R152a
                                 R143a
                                 R124
                                 R125
                                 R134
                                 R134a
                                 R32
 6
10
11
14
15
16
17
18
19

-------
IR1
IR
FO
XH
COP
VCR
PR
BTU/f t3
6
11
15
19
17
18
14
16
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
14
14
14
14
14
14
14
14
14
14
14
6
11
15
19
17
18
14
16
15
15
15
15
15
15
15
15
15
15
15
17
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
18
18
18
18
18
18
18
18
18
18
18
0
0
0
0
0
0
0
0
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
1
1
1
1
1
1
1
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
3.37
3.56
3.04
3.23
3.44
3.33
2.89
2.45
3.04
3.73
3.81
3.82
3.79
3.74
3.66
3.56
3.45
3.34
3.23
3.44
3.64
3.74
3.77
3.76
3.72
3.65
3.57
3.47
3.35
3.23
3.33
3.48
3.55
3.58
3.57
3.54
3.49
3.44
3.37
3.30
3.23
3.56
3.67
3.74
3.77
3.78
3.75
3.71
3.63
3.53
3.40
3.23
3.33
3.33
3.32
3.30
3.28
3.25
3.20
3.15
3.08
2.99
2.89
100.1
61.9
37.1
166.9
52.0
62.8
92.3
88.6
37.1
57.1
74.9
90.5
104.6
117.6
129.5
140.4
150.2
159.1
166.9
52.0
66.7
80.9
94.2
106.6
118.2
129.2
139.6
149.3
158.5
166.9
62.8
76.9
90.1
102.4
113.7
124.2
134.0
143.1
151.5
159.5
166.9
61.9
71.6
81.6
91.8
102.1
112.6
123.3
134.2
145.2
156.1
166.9
62.8
66.2
69.6
73.0
76.3
79.6
82.7
85.6
88.3
90.5
92.3
3.28
3.67
3.94
3.35
3.84
3.72
3.11
3.31
3.94
3.64
3.45
3.33
3.25
3.2
3.18
3.2
3.23
3.28
3.35
3.84
3.65
3.5
3.4
3.33
3.28
3.26
3.26
3.27
3.3
3.35
3.72
3.57
3.46
3.38
3.33
3.3
3.29
3.29
3.3
3.32
3.35
3.67
3.55
3.46
3.38
3.33
3.29
3.26
3.25
3.26
3.29
3.35
3.72
3.64
3.56
3.48
3.41
3.35
3.29
3.24
3.19
3.15
3.11
PSUC
psia
89.1
48.2
30.1
145.8
41.7
53.5
107.4
119.2
30.1
44.0
58.3
71.8
84.6
96.8
108.3
119.1
129.1
138.0
145.8
41.7
52.3
63.3
74.3
85.1
95.7
106.2
116.4
126.5
136.3
145.8
53.5
64.3
75.1
85.5
95.6
105.1
114.2
122.8
131.0
138.7
145.8
48.2
55.3
63.0
71.2
80.0
89.2
99.0
109.5
120.8
132.8
145.8
53.5
57.5
61.8
66.3
71.1
76.3
81.7
87.5
93.7
100.3
107.4
PDIS
psia
292
177
119
488
160
199
334
394
119
160
201
240
275
310
345
381
417
453
488
160
191
222
252
283
314
346
379
413
450
488
199
230
260
289
318
347
375
404
432
460
488
177
196
218
241
266
293
323
356
393
437
488
199
209
220
231
243
255
269
283
299
316
334
CLOAD
BTU/hr
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
1.1996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
WORK
Watt
1043
987
1157
1089
1023
1056
1218
1438
1157
944
922
921
928
940
960
986
1018
1053
1089
1023
966
941
933
936
946
962
985
1013
1048
1090
1056
1012
990
983
985
993
1006
1023
1043
1066
1090
987
957
940
932
931
937
949
968
996
1035
1090
1056
1056
1059
1064
1072
1083
1097
1117
1143
1176
1218
Tsup Tair
f C
189 78.8
173 78.8
147 78.8
227 78.8
148 78.8
152 78.8
151 78.8
146 78.8
147 78.8
157 78.8
170 78.8
180 78.8
188 78.8
194 78.8
200 78.8
206 78.8
213 78.8
220 78.8
227 78.8
148 78.8
159 78.8
169 78.8
177 78.8
185 78.8
192 78.8
199 78.8
206 78.8
213 78.8
220 78.8
227 78.8
152 78.8
161 78.8
169 78.8
177 78.8
184 78.8
191 78.8
198 78.8
205 78.8
213 78.8
220 78.8
227 78.8
173 78.8
178 78.8
184 78.8
189 78.8
194 78.8
200 78.8
205 78.8
210 78.8
215 78.8
221 78.8
227 78.8
152 78.8
152 78.8
152 78.8
153 78.8
153 78.8
153 78.8
153 78.8
153 78.8
152 78.8
152 78.8
151 78.8
14   11  -0.01
0  3.56
61.9  3.67   48.2   177  11996   987   173  78.8

-------
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
19
19
19
19
19
19
19
19
19
19
19
11
11
11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
3.57
3.57
3.56
3.53
3.50
3.44
3.36
3.25
3.10
2.89
3.04
3.30
3.53
3.57
3.55
3.51
3.45
3.36
3.23
3.08
2.89
3.33
3.33
3.32
3.30
3.26
3.21
3.14
3.04
2.91
2.72
2.45
3.56
3.57
3.58
3.57
3.55
3.51
3.45
3.35
3.19
2.92
2.45
3.04
3.17
3.28
3.37
3.45
3.49
3.42
3.30
3.12
2.85
2.44
3.97
4.85
4.95
4.95
4.92
4.87
4.78
4.66
4.52
4.36
4.20
64.7
67.7
70.8
74.2
77.6
81.1
84.6
88.0
90.7
92.3
37.1
44.2
51.4
58.2
64.7
70.8
76.6
81.8
86.3
89.9
92.3
62.8
65.8
69.0
72.4
75.8
79.3
82.8
85.9
88.5
89.8
88.6
61.9
64.5
67.3
70.4
73.9
77.6
81.5
85.6
89.5
91.8
88.6
37.1
42.8
48.9
55.3
61.8
68.4
74.9
81.1
86.5
89.8
88.6
40.4
62.9
81.9
98.3
113.0
126.6
139.2
150.8
161.4
171.0
179.3
3.6
3.53
3.46
3.4
3.34
3.28
3.23
3.18
3.14
3.11
3.94
3.74
3.58
3.47
3.37
3.29
3.22
3.17
3.14
3.11
3.11
3.72
3.67
3.61
3.56
3.51
3.46
3.42
3.38
3.34
3.32
3.31
3.67
3.61
3.56
3.51
3.46
3.41
3.37
3.33
3.3
3.29
3.31
3.94
3.82
3.71
3.62
3.53
3.46
3.39
3.34
3.3
3.29
3.31
3.17
2.91
2.79
2.71
2.66
2.62
2.61
2.62
2.65
2.7
2.76
51.3
54.7
58.5
62.9
67.8
73.4
79.8
87.4
96.4
107.4
30.1
36.0
42.4
49.2
56.3
63.7
71.5
79.7
88.4
97.6
107.4
53.5
57.0
60.9
65.2
70.1
75.6
81.8
89.0
97.4
107.3
119.2
48.2
50.9
53.9
57.5
61.7
66.6
72.6
79.9
89.3
101.7
119.2
30.1
34.7
39.9
45.8
52.5
59.9
68.4
78.1
89.4
102.9
119.2
30.1
45.0
59.5
72.9
85.6
97.6
109.0
119.6
129.4
138.2
145.8
184
193
203
214
226
241
258
278
303
334
119
135
152
171
190
210
231
253
277
304
334
199
209
220
232
246
262
280
301
326
356
394
177
184
192
202
213
227
245
266
295
335
394
119
132
148
166
185
207
232
261
295
338
394
96
131
166
198
227
256
284
313
343
373
402
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
985
986
989
995
1006
1022
1045
1080
11313
1218
115-7
1065
997
985
990
1001
1020
1048
10S7
1142
1218
1056
1057
1060
1067
1078
10S5
1119
1155
1209
1294
1438
987
984
983
984
990
1000
1019
1050
1103
1204
1438
1157
1109
1073
1043
1018
1006
1029
1065
1126
1233
1438
885
724
710
710
714
722
735
754
778
807
837
171
169
167
165
163
161
159
156
154
151
147
147
147
149
151
152
152
153
152
152
151
152
151
150
150
149
148
148
147
147
146
146
173
170
167
165
162
159
156
153
151
148
146
147
148
148
148
148
147
148
147
147
146
146
130
140
151
159
165
170
174
179
184
190
197
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
19   17  -0.01
0  4.42
56.4  3.11   41.7   130  11996    795    131  78.8

-------
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
4.72
4.85
4.90
4.89
4.84
4.76
4.66
4.53
4.37
4.20
4.32
4.53
4.64
4.68
4.67
4.63
4.57
4.49
4.40
4.30
4.20
4.54
4.70
4.81
4.87
4.88
4.86
4.80
4.72
4.59
4.42
4.20
4.32
4.34
4.35
4.35
4.33
4.30
4.26
4.20
4.13
4.03
3.91
4.54
4.56
4.58
4.59
4.58
4.55
4.51
4.43
4.32
4.15
3.91
3.97
4.34
4.64
4.70
4.70
4.66
4.59
4.49
4.34
4.15
3.91.
72.7
88.0
102.0
115.1
127.3
138.9
149.9
160.3
170.2
179.3
68.7
84.2
98.5
111.5
123.5
134.5
144.7
154.3
163.2
171.5
179.3
66.0
76.6
87.4
98.4
109.4
120.5
131.9
143.5
155.4
167.4
179.3
68.7
72.7
76.7
80.7
84.7
88.7
92.5
96.1
99.5
102.5
105.1
66.0
69.3
72.8
76.6
80.5
84.6
88.9
93.4
97.8
101.9
105.1
40.4
48.7
56.8
64.5
71.9
78.9
85.4
91.5
97.0
101.6
105.1
2.94
2.83
2.76
2.71
2.68
2.66
2.66
2.68
2.71
2.76
3.03
2.9
2.81
2.75
2.71
2.69
2.69
2.69
2.71
2.73
2.76
2.99
2.89
2.81
2.75
2.71
2.68
2.67
2.66
2.67
2.7
2.76
3.03
2.96
2.9
2.84
2.79
2.74
2.7
2.67
2.63
2.61
2.59
2.99
2.94
2.88
2.83
2.78
2.74
2.69
2.66
2.63
2.6
2.59
3.17
3.01
2.89
2.8
2.73
2.68
2.63
2.6
2.58
2.58
2.59
52.8
64.1
75.2
86.0
96.5
106.8
117.0
126.9
136.5
145.8
53.5
64.7
75.8
86.3
96.3
105.8
114.8
123.3
131.3
138.8
145.8
48.2
55.6
63.5
71.9
80.7
89.9
99.7
110.1
121.2
133.1
145.8
53.5
57.6
62.0
66.6
71.5
76.7
82.1
87.9
94.0
100.5
107.4
48.2
51.4
54.9
58.8
63.2
68.2
73.8
80.3
87.8
96.7
107.4
30.1
36.4
43.0
50.0
57.1
64.6
72.3
80.5
89.0
97.9
107.4
155
181
207
233
258
285
312
340
370
402
162
187
213
237
261
285
309
332
355
379
402
144
161
179
198
219
241
266
293
324
359
402
162
170
180
189
199
210
222
234
248
262
278
144
151
158
166
176
187
199
213
231
252
278
96
109
124
140
156
173
191
209
230
252
278
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11 996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
746
724
718
720
727
738
755
777
804
837
813
775
757
752
753
760
770
783
799
817
837
775
747
731
722
720
724
732
745
765
794
837
813
810
808
809
811
817
825
836
852
873
900
775
770
767
766
767
772
780
793
815
848
900
885
810
757
747
748
754
766
784
810
847
900
140
148
155
162
167
173
178
184
190
197
134
142
149
155
161
167
173
178
184
190
197
152
156
161
165
170
174
178
182
187
191
197
134
134
134
134
134
134
134
134
134
133
132
152
150
148
147
145
143
142
140
137
135
132
130
130
130
132
134
135
135
135
134
134
132
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
,78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
16   18  -0.01
                   0  3.33
                               62.8  3.72    53.5    199  11996  1056   152  78.8

-------
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
14
14
14
14
14
14
14
14
14
14
14
14
18
18
18
18
18
18
18
18
18
18
11
11
11
, 11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
18
18
18
18
18
18
18
18
18
18
18
11
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
rO.01
-0.01
-0.01
-0.01
-0.01
-0.01
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
3.33
3.32
3.30
3.26
3.21
3.14
3.04
2.91
2.72
2.45
3.56
3.57
3.58
3.57
3.55
3.51
3.45
3.35
3.19
2.92
2.45
3.04
3.17
3.28
3;37
3.45
3.49
3.42
3.30
3.12
2.85
2.44
2.60
2.74
2.82
2.84
2.84
2.81
2.78
2.73
2.68
2.62
2.56
2.83
2.93
2.99
3.02
3.03
3.01
2.96
2.90
2.81
2.70
2.56
2.60
2.60
2.59
2.57
2.55
2.52
2.48
2.43
2.36
2.29
2.19
2.83
65.8
69.0
72.4
75.8
79.3
82.8
85.9
88.5
89.8
88.6
61.9
64.5
67.3
70.4
73.9
77.6
81.5
85.6
89.5
91.8
88.6
37.1
42.8
48.9
55.3
61.8
68.4
74.9
81.1
86.5
89.8
88.6
42.7
52.6
62.0
70.9
79.2
87.1
94.5
101.5
108.2
114.5
120.4
42.8
49.5
56.5
63.7
71.0
78.6
86.4
94.5
102.9
111.6
120.4
42.7
45.1
47.5
50.0
52.5
54.9
57.3
59.6
61.7
63.5
65.0
42.8
3.67
3.61
3.56
3.51
3.46
3.42
3.38
3.34
3.32
3.31
3.67
3.61
3.56
3.51
3.46
3.41
3.37
3.33
3.3
3.29
3.31
3.94
3.82
3.71
3.62
3.53
3.46
3.39
3.34
3.3
3.29
3.31
5.14
4.88
4.69
4.55
4.47
4.42
4.39
4.39
4.4
4.42
4.46
5.01
4.81
4.65
4.53
4.44
4.38
4.34
4.33
4.34
4.38
4.46
5.14
5.01
4.88
4.76
4.65
4.55
4.46
4.38
4.3
4.23
4.17
5.01
57.0
60.9
65.2
70.1
75.6
81.8
89.0
97.4
107.3
119.2
48.2
50.9
53.9
57.5
61.7
66.6
72.6
79.9
89.3
101.7
119.2
30.1
34.7
39.9
45.8
52.5
59.9
68.4
78.1
89.4
102.9
119.2
36.7
44.0
51.4
58.7
65.9
72.8
79.6
86.1
92.4
98.4
104.0
33.1
37.9
43.1
48.7
54.7
61.2
68.2
75.9
84.4
93.7
104.0
36.7
39.6
42.6
46.0
49.5
53.3
57.5
61.9
66.8
72.1
78.0
33.1
209
220
232
246
262
280
301
326
356
394
177
184
192
202
213
227
245
266
295
335
394
119
132
148
166
185
207
232
261
295
338
394
189
214
241
267
294
322
350
378
407
435
464
166
182
200
221
243
268
296
329
366
411
464
189
198
208
219
230
243
256
271
287
305
325
166
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
. 11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
1057
1061)
1067
1071J
10915
11V.?
11515
1200
1294
1433
987
984
983
984
99!)
1000
1019
10513
110:5
1204
14313
1157
1109
107.5
1043
1018
1006
1029
10615
1126
1233
14313
1350
128)
12413
1236
12313
12413
1265
1287
1312
1340
1370
1241
1199
1174
1162
1161
1169
1186
1212
12510
1301
137iO
1350
1352
13513
1366
1379
1396
1419
14413
1487
1536
1601
1241
151 78.8
150 78.8
150 78.8
149 78.8
148 78.8
148 78.8
147 78.8
147 78.8
146 78.8
146 78.8
173 78.8
170 78.8
167 78.8
165 78.8
162 78.8
159 78.8
156 78.8
153 78.8
151 78.8
148 78.8
146 78.8
147 78.8
148 78.8
148 78.8
148 78.8
148 78.8
147 78.8
148 78.8
147 78.8
147 78.8
146 78.8
146 78.8
155 46.99
165 46.99
175 46.99
184 46.99
193 46.99
202 46.99
211 46.99
220 46.99
229 46.99
239 46.99
249 46.99
181 46.99
187 46.99
192 46.99
198 46.99
204 46.99
211 46.99
217 46.99
225 46.99
232 46.99
240 46.99
249 46.99
155 46.99
155 46.99
156 46.99
156 46.99
156 46.99
156 46.99
156 46.99
156 46.99
156 46.99
156 46.99
155 46.99
181 46.99


-------
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
16
19
19
19
19
19
19
19
19
19
19
19
19
11
11
11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
17
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0,6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4-
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
2.83
2.83
2.81
2.79
2.75
2.70
2.63
2.53
2.39
2.19
2.41
2.64
2.79
2.80
2.79
2.75
2.69
2.60
2.49
2.36
2.19
2,60
2.60
2.58
2.56
2.53
2.48
2.41
2.32
2.19
2.00
1.71
2.83
2.84
2.84
2.83
2.81
2.77
2,71
2.61
2.46
2.21
1.71
2.41
2.52
2.62
2.69
2.74
2.75
2.67
2.56
2.38
2.13
1.71
2.41
3.00
3.09
3.09
3.05
2.99
2.92
2.83
2.74
2.65
2.56
2.70
44.8
46.9
49.1
51.5
54.0
56.6
59.2
61.7
63.9
65.0
24.6
29.5
34.4
39; 1
43.7
48.1
52.4
56.3
59.9
62.9
65.0
42.7
44.7
46.9
49.2
sns
53.9
56.3
58,4
60.0
60.3
57.6
42.8
44.6
46.5
48.6
50.9
53.5
56.2
59.0
61.5
62.7
57.6
24.6
28.4
32.5
36.8
41.2
45.7
50.2
54.5
58.2
60.4
57.6
24.6
38.2
50.3
61.0
71.0
80.6
89.8
98.6
106.7
114.1
120.4
35.0
4.9
4.79
4.69
4.6
4.5
4.42
4.34
4.27
4.21
4.17
5.55
5.19
4.92
4.74
4.59
4.46
4.36
4.28
4.23
4.19
4,17
5.14
5.05
4.97
4.89
4.81
4.74
4.68
4.63
4.6
4.6
4.66
5.01
4.92
4.84
4.76
4.69
4.62
4.56
4.51
4.48
4.5
4.66
5.55
5.33
5.14
4.97
4.83
4.71
4.63
4.56
4.52
4.54
4.66
5.55
4.92
4.62
4.45
4.34
4.28
4.25
4.26
4.31
4.37
4.46
5.34
35.3
37.7
40.5
43.6
47.1
51.3
56.1
61.9
69.1
78.0
20.4
24.2
28.5
33.1
38.1
43.4
49.1
55.3
62.1
69.7
78.0
36.7
39.1
41.8
44,9
48.3
52.3
56.8
62.2
68.5
76.2
85.8
33.1
35.0
37.1
39.6
42.5
45.9
50.2
55.5
62.5
71.9
85.8
20.4
23.3
26.7
30.6
35.1
40.2
46.1
53.1
61.6
72.2
85.8
20.4
29.2
38.4
47.4
56.2
65.0
73.8
82.3
90.4
97.8
104.0
28.3
173
181
190
200
212
227
244
265
291
325
113
126
140
157
175
194
214
237
263
292
325
189
198
208
219
233
248
266
288
315
350
400
166
172
180
188
199
212
229
250
280
323
400
113
124
137
152
169
189
213
242
279
328
400
113
144
177
211
244
278
314
351
389
427
464
151
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
1241
1244
1250
1260
1277
1301
1336
1389
1469
1601
1460
1331
1258
1253
1260
1279
1308
1350
1408
1488
1601
1350
1353
1359
1371
1389
1416
1455
1513
1604
1753
2059
1241
1238
1238
1242
1251
1268
1296
1344
1427
1591
2059
1460
1392
1343
1307
1282
1279
1315
1375
1473
1651
2059
1460
1172
1136
1137
1152
1174
1204
1239
1280
1324
1370
1303
178 46.99
176 46.99
173 46.99
171 46.99
168 46.99
166 46.99
163 46.99
161 46.99
158 46.99
155 46.99
149 46.99
147 46.99
147 46.99
149 46.99
151 46.99
153 46.99
154 46.99
155 46.99
155 46.99
155 46.99
155 46.99
155 46.99
154 46.99
153 46.99
152 46.99
151 46.99
150 46.99
150 46.99
149 46.99
149 46.99
149 46.99
151 46.99
181 46.99
177 46.99
174 46.99
170 46.99
167 46.99
163 46.99
159 46.99
156 46.99
152 46.99
150 46.99
151 46.99
149 46.99
148 46.99
148 46.99
147 46.99
146 46.99
146 46.99
146 46.99
147 46.99
147 46.99
148 46.99
151 46.99
149 46.99
157 46.99
171 46.99
182 46.99
192 46.99
202 46.99
211 46.99
220 46.99
229 46.99
238 46.99
249 46.99
151 46.99

-------
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
14
14
14
14
14
14
14
14
14
14
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
19
14
14
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
11
11
11
11
11
11
11
11
11
11
11
18
18
18
18
18
18
18
18
18
18
17
17
17
17
17
17
17
17
17
17
17
15
15
15
15
15
15
15
15
15
15
15
11
11
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0,01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0
0.1
2.89
2.98
3.01
3.00
2.97
2.91
2.84
2.76
2.66
2.56
1.45
1.56
1.62
1.64
1.65
1.64
1.62
1.60
1.57
1.54
1.51
1.70
1.75
1.79
1.81
.81
.79
.76
.72
.67
.60
.51
.45
.44
.42
.39
.36
1.33
1.28
1.23
1.16
1.06
1.54
1.67
1.74
1.77
1.77
1.75
1.72
1.67
1.63
1.57
1.51
1.40
1.73
1.81
.83
.81
.77
.72
.67
.61
.56
.51
.70
.68
45.1
55.0
64.3
73.2
81.8
90.1
98.1
105.9
113.4
120.4
19.0
24.0
29.0
33.9
38.6
43.0
47.3
51.4
55.3
58.9
62.4
20.7
24.0
27.6
31.4
35.4
39.5
43.8
48.2
52.9
57.6
62.4
19.0
20.1
21.2
22.3
23.3
24.3
25.3
26.1
26.5
26.4
15.6
20.5
25.6
30.6
35.6
40.4
45.0
49.6
54.1
58.3
62.4
10.6
17.1
23.3
29.3
34.8
40.1
45.2
50.1
54.7
58.9
62.4
20.7
21.6
4.99
4.74
4.58
4.47
4.4
4.36
4.35
4.37
4.4
4.46
11,72
10.94
10.34
9.9
9.59
9.38
9.24
9.17
9.14
9.14
9.18
10.96
10.48
10.06
9.72
9.45
9.24
9.11
9.03
9.02
9.06
9.18
11.72
11.36
11.03
10.72
10.42
10.15
9.91
9.7
9.53
9.45
12.3
11.34
10.58
10.01
9.63
9.37
9.21
9.12
9.1
9.12
9.18
13.04
11.29
10.23
9.58
9.21
9
8.9
8.89
8.92
9.02
9.18
10.96
10.69
35.2
42.6
50.0
57.6
65.2
72.9
80.6
88.5
96.3
104.0
18.8
22.5
26.5
30.6
34.7
38.8
42.8
46.7
50.5
54.1
57.5
17.1
19.5
22.2
25.3
28.6
32.3
36.3
40.7
45.7
51.2
' 57.5
18.8
20.4
22.1
23.9
26.0
28.3
30.8
33.5
36.6
40.2
14.2
17.6
21.5
25.6
29.8
34.2
38.7
43.3
48.0
52.8
57.5
10.1
14.3
19.2
24.3
29.3
34.4
39.4
44.5
49.3
53.8
57.5
17.1
18.3
176
202
229
257
287
318
351
386
424
464
220
246
274
303
333
364
396
428
461
495
528
187
204
224
246
270
298
330
368
412
465
528
220
231
243
257
271
287
305
325
349
380
175
199
227
256
287
321
356
395
437
481
528
132
161
196
232
270
309
351
395
440
485
528
187
195
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
12116
1178
1166
1170
112)4
1207
122J7
1274
1319
1370
24116
2255
2175
21218
2130
2140
2163
2195
2234
22/7
23?.5
2071
20CI5
1965
1946
1944
1959
1991
2039
2108
2201
2325
2416
2444
247'8
2521
257'6
2645
2735
2856
302:7
3302
2279
2103
202.1
1988
198,7
2008
2046
2098
2162
2238
2325
2517
2035
1940
1924
1946
1989
2045
2109
2178
2249
2325
2071
2087
162 46.99
172 46.99
182 46.99
191 46.99
201 46.99
210 46.99
219 46.99
229 46.99
239 46.99
249 46.99
184 17.01
198 17.01
211 17.01
224 17.01
238 17.01
251 17.01
265 17.01
278 17.01
292 17.01
307 17.01
321 17.01
221 17.01
229 17.01
237 17.01
246 17.01
255 17.01
264 17.01
274 17.01
285 17.01
296 17.01
309 17.01
321 17.01
184 "17.01
185 17.01
186 17.01
186 17.01
187 17.01
187 17.01
188 17.01
189 17.01
190 17.01
191 17.01
178 17.01
193 17.01
207 17.01
221 17.01
235 17.01
249 17.01
263 17.01
278 17.01
292 17.01
307 17.01
321 17.01
170 17.01
184 17.01
202 17.01
219 17.01
234 17.01
249 17.01
264 17.01
278 17.01
292 17.01
306 17.01
321 17.01
221 17.01
217 17.01

-------
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
11
11
11.
11
11
11
11
11
15
15
15
15
15
15
15
15
15
15
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.67
1.64
1.61
1.57
1.52
1.45
1.35
1.21
1.40
1.53
1.54
1.54
1.52
1.49
1.43
1.36
1.27
1.14
22.5
23.5
24.6
25.7
26.8
27.7
28.4
28.4
10.6
12.8
15.0
17.1
19.3
21.4
23.3
25.0
26.3
26.8
10.44
10.19
9.95
9.72
9.51
9.32
9.17
9.12
13.04
12.05
11.41
10.87
10.4
10.02
9.71
9.47
9.31
9.27
19.6
21.1
22.8
24.9
27.3
30.2
33.7
38.3
10.1
1Z.O
14.2
16.6
19.3
22.3
25.6
29.4
33.6
38.5
204
215
227
242
259
281
309
349
132
145
162
181
201
224
249
278
313
357
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
11989
2110
2140
2181
2236
2314
2427
2601
2914
2517
2303
2275
2278
2308
2365
2453
2581
2775
3096
214 17.01
210 17.01
206 17.01
203 17.01
200 17.01
196 17.01
193 17.01
191 17.01
170 17.01
168 17.01
172 17.01
175 17.01
178 17.01
180 17.01
182 17.01
185 17.01
187 17.01
189 17.01

-------
                                         APPENDIX #3
This appendix contains a listing of the short output files for all computer runs conducted for ternary mixtures.
The refrigerants arc specified by code numbers according to the following table.
                                         R22
                                         R142b
                                         R152a
                                         R143a
                                         R124
                                         R125
                                         R134
                                         R134a
                                         R32
6
10
11
14
15
16
17
18
19

-------
IR1 IR2
IR3
F01
F02
F03
X1
X2
X3
COP Vol. Flow
PR
ft3
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
17
17
17
17
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
rO.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0
0
0
0
0
0
0
0
0
0
0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.6
0.6
0.6
0.6
0.7
0.7
0.7
0.7
0.8
0.8
0.8
0.9
0.9
1
0
0
0
0
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.2
0.1
0
0
0.1
0
1
0.9
0.8
0.7
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.1
0
0
0
0.1
0.2
0.3
3.56
3.57
3.58
3.58
3.58
3.58
3.56
3.54
3.51
3.39
3.04
3.72
3.74
3.75
3.75
3.75
3.74
3.72
3.71
3.69
3.67
3.74
3.76
3.78
3.80
3.82
3.83
3.83
3.83
3.81
3.82
3.83
3.84
3.84
3.83
3.81
3.79
3.77
3.78
3.79
3.80
3.81
3.81
3.81
3.79
3.74
3.76
3.77
3.77
3.76
3.75
3.70
3.71
3.70
3.69
3.66
3.56
3.60
3.62
3.63
3.53
3.50
3.45
3.34
3.40
3.23
3.56
3.56
3.56
3.55
40.8
41.9
43.1
44.5
46.1
48.1
50.4
53.3
56.9
61.7
68.2
44.3
42.5
41.0
39.8
38.8
37.9
37.1
36.4
35.8
35.3
31.0
31.2
31.4
31.7
32.0
32.3
32.7
33.2
33.7
27.9
27.8
27.7
27.7
27.6
27.6
27.6
27.5
24.7
24.6
24.5
24.4
24.3
24.2
24.1
21.5
21.7
21.9
22.1
22.3
22.4
20.5
20.3
20.0
19.8
19.5
18.0
18.3
18.6
18.8
17.4
17.1
16.8
15.9
16.2
15.1
40.8
41.5
42.2
42.9
3.7
3.7
3.7
3.7
3.7
3.7
3.7
3.7
3.8
3.8
3.9
3.6
3.6
3.6
3.5
3.5
3.5
3.5
3.5
3.5
3.6
3.5
3.4
3.4
3.4
3.4
3.4
3.4
3.4
3.5
3.3
3.3
3.3
3.3
3.3
3.4
3.4
3.4
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.2
3.2
3.2
3.2
3.3
3.3
3.3
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.2
3.3
3.2
3.2
3.3
3.3
3.3
3.7
3.7
3.7
3.7
PSUC PDIS
psia psia
48.2
47.0
45.7
44.3
42.8
41.2
39.4
37.4
35.2
32.8
30.1
44.0
45.9
47.5
49.0
50.3
51.5
52.5
53.5
54.4
55.3
63.0
62.6
62.1
61.6
61.1
60.5
59.8
59.1
58.3
71.8
71.7
71.6
71.5
71.4
71.3
71.3
71.2
80.0
80.5
81.1
81.9
82.7
83.6
84.6
96.8
94.9
93.2
91.7
90.4
89.2
99.0
100.9
103.1
105.5
108.3
119.1
115.5
112.3
109.5
120.8
124.6
129.1
138.0
132.8
145.8
48.2
47.4
46.6
45.8
177
172
168
163
158
152
146
140
133
126
119
160
165
169
173
178
182
186
189
193
196
218
215
213
211
209
206
204
203
201
240
238
238
238
238
239
240
241
266
266
267
268
270
272
275
310
305
301
298
295
293
323
327
332
338
345
381
371
363
356
393
404
417
453
437
488
177
175
172
170
CAP WORK Tair
BTU/hr
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
watt
987
984
982
981
981
983
986
992
1001
1036
1157
944
939
937
937
938
941
944
948
953
957
940
934
929
925
921
919
918
918
922
921
917
916
916
919
922
927
932
931
927
924
922
922
923
928
941
936
934
933
934
937
949
949
950
954
960
986
977
971
968
996
1005
1018
1053
1035
1090
987
987
988
989
F
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8

-------
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
17 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
18 -0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0
0
0
0
0
0
0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.6
0.6
0.6
0.6
0.7
0.7
0.7
0.7
0.8
0.8
0.8
0.9
0.9
1
0
0
0
0
0
0
0
0
0
0
0.6 0.4
0.5 0.5
0.4 0.6
0.3 0.7
0.2 0.8
0.1 0.9
0 1
0 0.9
0.1 0.8
0.2 0.7
0.3 0.6
0.4 0.5
0.5 0.4
0.6 0.3
0.7 0.2
0.8 0.1
0.9 0
0.8 0
0.7 0.1
0.6 0.2
0.5 0.3
0.4 0.4
0.3 0.5
0.2 0.6
0.1 0.7
0 0.8
0 0.7
0.1 0.6
0.2 0.5
0.3 0.4
0.4 0.3
0.5 0.2
0.6 0.1
0.7 0
0.6 0
0.5 0.1
0.4 0.2
0.3 0.3
0.2 0.4
0.1 0.5
0 0.6
0 0.5
0.1 0.4
0.2 0.3
0.3 0.2
0.4 0.1
0.5 0
0.4 0
0.3 0.1
0.2 0.2
0.1 0.3
0 0.4
0 0.3
0.1 0.2
0.2 0.1
0.3 0
0.2 0
0.1 0.1
0 0.2
0 0.1
0.1 0
0 0
1 0
0.9 0.1
0.8 0.2
0.7 0.3
0.6 0.4
0.5 0.5
0.4 0.6
0.3 0.7
0.2 0.8
0.1 0.9
3.54
3.53
3.52
3.50
3.49
3.46
3.44
3.64
3.65
3.67
3.68
3.68
3.68
3.68
3.68
3.68
3.67
3.74
3.75
3.76
3.76
3.76
3.76
3.76
3.75
3.73
3.77
3.78
3.79
3.79
3.79
3.79
3.78
3.77
3.78
3.78
3.79
3.79
3.78
3.77
3.76
3.72
3.74
3.75
3.76
3.76
3.75
3.70
3.70
3.69
3.68
3.65
3.57
3.60
3.62
3.63
3.53
3.51
3.47
3.35
3.40
3.23
3.56
3.55
3.54
3.53
3.51
3.49
3.47
3.45
3.42
3.38
43.7
44.5
45.3
46.2
47.0
47.8
48.6
37.9
37.7
37.5
37.2
36,9
36.6
36.3
36.0
35.6
35.3
31.0
31.1
31.2
31.3
31.3
31.4
31.4
31.3
31.2
26.8
27.0
27.2
27.3
27.4
27.5
27.5
27.5
24.7
24.6
24.5
24.3
24.2
24.0
23.7
21.4
21.6
21.9
22.1
22.3
22.4
20.5
20.3
20.1
19.8
19.6
18.1
18.4
18.6
18.8
17.4
17.2
16.9
15.9
16.2
15.1
40.8
40.9
41.0
41.1
41.1
41.1
41.1
40.9
40.8
40.5
3.7 45.0
3.8 44.3
3.8 43.6
3.8 43.0
3.8 42.5
3.8 42.0
3.8 41.7
3.6 52.3
3.6 52.2
3.6 52.3
3.6 52.5
3.6 52.8
3.6 53.2
3.6 53.7
3.6 54.2
3.6 54.7
3.6 55.3
3.5 63.0
3.5 62.7
3.5 62.5
3.5 62.3
3.5 62.2
3.5 62.2
3.5 62.4
3.5 62.7
3.5 63.3
3.4 74.3
3.4 73.3
3.4 72.5
3.4 72.0
3.4 71.6
3.4 71.4
3.4 71.2
3.4 71.2
3.3 80.0
3.3 80.3
3.3 80.9
3.3 81.6
3.3 82.5
3.3 83.6
3.3 85.1
3.3 95.7
3.3 93.8
3.3 92.2
3.3 91.0
3.3 90.0
3.3 89.2
3.3 99.0
3.3 100.3
3.3 101.9
3.3 103.8
3.3 106.2
3.3 116.4
3.3 113.7
3.2 111.4
3.2 109.5
3.3 120.8
3.3 123.4
3.3 126.5
3.3 136.3
3.3 132.8
3.3 145.8
3.7 48.2
3.7 48.2
3.7 48.3
3.7 48.5
3.7 48.7
3.7 49.1
3.7 49.6
3.7 50.2
3.7 51.0
3.7 52.1
16&
166
165
163
162!
. 161
16(1
191
190
189
190
19(1
191
192
19:;
195
196
21»
217
217
216
216
217
21!!
219
222
252
249
246
244
243
242
241
241
266
267
269
271
274
27«
283
314
308
303
299
296
293
323
327
33I2
33I3
346
379
370
362
356
393
402
414
450
437
483
177
177
178
179
180
182
184
186
190
194
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
992 78.8
995 78.8
998 78.8
1003 78.8
1008 78.8
1015 78.8
1023 78.8
967 78.8
962 78.8
959 78.8
956 78.8
955 78.8
954 78.8
954 78.8
955 78.8
956 78.8
957 78.8
940 78.8
938 78.8
936 78.8
935 78.8
934 78.8
934 78.8
935 78.8
938 78.8
941 78.8
933 78.8
930 78.8
928 78.8
927 78.8
927 78.8
928 78.8
929 78.8
932 78.8
931 78.8
929 78.8
928 78.8
928 78.8
929 78.8
932 78.8
936 78.8
946 78.8
941 78.8
938 78.8
936 78.8
936 78.8
937 78.8
949 78.8
949 78.8
952 78.8
956 78.8
962 78.8
985 78.8
976 78.8
971 78.8
968 78.8
996 78.8
1003 78.8
1013 78.8
1049 78.8
1035 78.8
1090 78.8
987 78.8
990 78.8
993 78.8
997 78.8
1002 78.8
1007 78.8
1013 78.8
1020 78.8
1029 78.8
1041 78.8

-------
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
19 11
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
•0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
-0.01
0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.6
0.6
0.6
0.6
0.7
0.7
0.7
0.7
0.8
0.8
0.8
0.9
0.9
1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.2
0.1
0
0
0.1
0
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.1
0
0
3.33
3.47
3.52
3.56
3.59
3.61
3.63
3.64
3.65
3.66
3.67
3.74
3.73
3.72
3.71
3.69
3.67
3.64
3.60
3.55
3.58
3.63
3.68
3.71
3.73
3.75
3.76
3.77
3.78
3.76
3.74
3.71
3.68
3.63
3.57
3.54
3.61
3.66
3.70
3.73
3.75
3.70
3.67
3.63
3.57
3.49
3.43
3.52
3.58
3.63
3.53
3.46
3.37
3.30
3.40
3.23
40.2
32.9
33.3
33.7
34.1
34.4
34.7
34.9
35.0
35.2
35.3
31.0
30.7
30.5
30.1
29.8
29.4
29.0
28.5
28.0
24.7
25.2
25.6
26.1
26.5
26.9
27.2
27.5
24.7
24.4
24.0
23.6
23.1
22.7
22.2
20.3
20.8
21.2
21.6
22.1
22.4
20.5
20.1
19.7
19.3
18.9
17.7
18.1
18.4
18.8
17.4
17.0
16.7
15.8
16.2
15.1
3.7
3.6
3.6
3.6
3.6
3.6
3.6
3.6
3.6
3.6
3.6
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.4
3.4
3.4
3.4
3.4
3.4
3.4
3.4
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.3
3.2
3.3
3.3
3.3
3.3
3.3
3.3
53.5
64.3
62.2
60.6
59.3
58.3
57.4
56.7
56.1
55.7
55.3
63.0
63.8
64.7
65.7
67.0
68.5
70.3
72.4
75.1
85.5
82.3
79.6
77.4
75.5
73.8
72.4
71.2
80.0
81.7
83.6
85.9
88.6
91.8
95.6
105.1
100.8
97.2
94.2
91.5
89.2
99.0
102.0
105.4
109.5
114.2
122.8
117.7
113.3
109.5
120.8
125.5
131.0
138.7
132.8
145.8
199
230
222
216
212
208
205
202
200
198
196
218
221
224
227
232
237
243
250
260
289
278
269
261
255
250
245
241
266
272
278
286
294
305
318
347
332
320
309
301
293
323
333
344
358
375
404
385
369
356
393
411
432
460
437
488
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
11996
1056
1012
997
987
979
973
969
965
962
959
957
940
942
944
948
952
958
965
976
990
983
968
956
948
942
938
934
932
931
935
940
946
956
968
985
994
974
960
950
942
937
949
957
969
985
1007
1024
999
981
968
996
1016
1044
1066
1035
1090
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
78.8
Government Printing Office :  1992 - 312-014/40059

-------

-------

-------


-------
At-

-------