Emerging Refrigerants and Retrofit Options for Air Conditioning and Refrigeration

Selvaraji Muthu DGM-NTD, Subros Limited, C-51, Phase-2, Noida, U.P. selvaraji.muthu@subros.com +91- 9910307727 Aseem Kumar Jaiswal VP R&D, NTD, Subros Limited, C-51, Phase-2, Noida, U.P. ajaiswal@subros.com +91- 9810435765 Presentation at ACR Trendz 18th & 19th Oct 2013 by ISHRAE Pune Chapter Le Meridian , Pune
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Flow of Presentation: 1. Introduction 2. Refrigerant Properties 3. Types of Refrigerants 4. Generation of Refrigerants 5. What is ODP? 6. Montreal Protocol 7. What is GWP? 8. What is TEWI? 9. Kyoto Protocol 10.Fourth generation Refrigerants 11.Retrofit options 12. Reefer trucks 13.Future technology options 14.Conclusion 15.References
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1. Introduction
C1 to D : Compression (Polytrophic)

D to E : De-super heating (Isobaric) E to A : Condensation (Isobaric, Isothermal) A to A1 : Sub-cooling (Isobaric)

A1 to B : Expansion (throttling, Isenthalpic)

B to C : Evaporation (Isobaric, Isothermal) C to C1 : Super heating (Isobaric)

Vapour Compression refrigeration Circuit

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Types of Compressors

2. Refrigerant Properties
Required Properties of Ideal Refrigerant: 1) Low boiling point and Low freezing point. 2) Low specific heat and High latent heat. 3) High critical pressure and temperature 4) Low specific volume to reduce the size of the compressor. 5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser. 6) Non-flammable, non-explosive, non-toxic and non-corrosive. 7) High miscibility with lubricating oil 8) High COP in the working temperature range. 9) Compatible with legal requirement 10) Availability and cost

Numbering Logic for Refrigerants

R()13 4 a isomer # of fluorine atoms per molecule # of hydrogen atoms + 1 per molecule

# of carbon atoms -1 per molecule (left off when 0) # of unsaturated carbon bonds (left off when 0)

Decoding of Refrigerants

R134+90 =( ) 2 2 4 R1234+90=(1)3 2 4 # of Fluorine atoms per molecule # of Hydrogen atoms per molecule # of Carbon atoms per molecule # of unsaturated carbon bonds (left off when 0) # of Chlorine atoms per molecule (calculated from balance carbon bonding
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3. Types of Refrigerants
Methane Group Ethane Group Propane Zeotrope group mixtures Azeotrope organic mixtures compounds inorga nic compo unds 700 Series Series with isolated carbon > 1000 Series as per Numbering Logic R1100s R1200s R1234ze R1234yf R1270 etc

10 Series

100 Series

200 Series

400 Series

500 Series

600 Series

as per Numbering Logic R11 R123

Numbering Convention does not work

R404a

600 R717Hydrocarbons ammon ia NH3 R507c 610 Oxygen compounds 620 Sulfur compounds etc.. 630 Nitrogen compounds R718water R744CO2 R729 Air

R12 R22 etc..

R134a

R407c R410a

etc..

etc..

etc..

Grouping of Refrigerants
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Zeotropic refrigerants : Boil at different temperatures Azeotropic refrigerants : Boil at constant temperature
8

Classification of Refrigerants

4. Generations of refrigerants
1st Generation of refrigerants First generation refrigerants, used for almost one hundred years (1830 ~ 1930 ), were a variety of volatile compounds ( ethers,CO2,NH3, SO2,HCs,H2O,CCL2,CHCs etc. ) that exhibited useful characteristics.

Ammonia (NH3), methyl chloride (CH3Cl), and sulfur dioxide (SO2) are toxic gases. Several fatal accidents occurred in the 1920s because of methyl chloride leakage from refrigerators, which pushed the entire world to look for next generation refrigerants.

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Generations of refrigerants 2nd Generation of refrigerants Emphasising the need for improved endurance and safety. CFCs (1930s) and later HCFCs (1940s) were invented by Thomas Midgley Jr. (aided by Charles Franklin Kettering

As per the patent no. 2104882 (1931) of Thomas Midgley Jr.,

CnHmFpXr

in which

C - Carbon n is No. of carbon atoms, one or more. H - Hydrogen m is No. of Hydrogen atoms F - Fluorine p is No. of Fluorine atoms, one or more X - Chlorine, bromine or iodine or combinations thereof r is the total number of such atoms. r may be zero when p is greater than one

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Methane (R50)
Molecular Weight , kg/kmol C H = 12 = 1.01

H
Molecular Weight = 1*12+4*1.01 = 16.04 kg/kmol Boiling Point = - 161 o C Density = 716 g/cc

C
CH4

R12
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904 Produced in 1931

Cl

CnHmFpXr
n=1 m=0 p=2 x=Cl r=2

F
Molecular Weight = 1*12+2*35.453+2*18.998 = 120.9 kg/kmol Boiling Point = - 29.8 o C Density = 1.486 g/cc

C
CCl2F2

Cl

DiChloro-DiFluoro-Methane

R11
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904 Produced in 1932

Cl

CnHmFpXr
n=1 m=0 p=1 x=Cl r=3

Cl
Molecular Weight = 1*12+3*35.453+1*18.998 = 137.36 kg/kmol Boiling Point = + 23.77 o C Density = 1.494 g/cc

C
CCl3F

Cl

TriChloro-Fluoro-Methane

R22
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

Cl

CnHmFpXr
n=1 m=1 p=2 x=Cl r=1

F
Molecular Weight = 1*12+1*1.01+1*35.453+2*18.998 = 86.46 kg/kmol Boiling Point = - 40.7 o C Density = 3.66 g/cc

C
H

F
CHClF2

DiFluoro-Chloro-Methane

Generations of refrigerants

3rd generation of refrigerants includes chemical groups, such as hydro-fluoro-carbons (HFCs), that do not damage the ozone layer as that was the perceived environmental danger at the time. However, as the effects of refrigerant leakages on global warming and climate change have become evident, next generation refrigerants are required.

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Ethane (R 170)
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

C
H

C
C2H6
Ethane

Molecular Weight = 2*12+6*1.01 = 30.06 kg/kmol Boiling Point = - 89 o C Density = 1.282 g/cc

R134a
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

CnHmFpXr

n=2 m=2 p=4 x=Cl r=0

C
F

C
F
C2H2F4

Molecular Weight = 2*12+2*1.01+4*18.998 = 102.1 kg/kmol Boiling Point = - 26.3 o C Density = 0.00425g/cc

Generations of refrigerants 4th generation of refrigerants The `synthetic refrigerants' such as HFCs are being replaced with HFOs or `natural refrigerants.

Hydro Olefins:

HFO R1234ze HFO R1234yf Natural refrigerants: CO2 Organic gases R290 (Propane), R600a (Isobutane), R1270 (Propolene)

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Propene (R1270)
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

H
Molecular Weight = 3*12+6*1.01 = 42.06 kg/kmol Boiling Point = - 47.6 o C Density = 1.81g/cc

C C C
C3H6

Propylene

R1234-yf
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

CnHmFpXr

n=3 m=2 p=4 x=Cl r=0

F
Molecular Weight = 3*12+2*1.01+4*18.998 = 114.01 kg/kmol Boiling Point = - 30 o C Density = 1.1 g/cc

C C C
C3H2F4

TetraFluoroPropene

Four generations (Calm JM, 2010).

Low ozone depletion potential (ODP) low global warming potential (GWP) short atmospheric lifetime (tatm) high efficiency.
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5. What is ODP?
ODP is Ozone Depletion Potential of with reference to CFC R11 as 1. Cl + O3 -> ClO + O2 ClO + O3 -> Cl + 2O2
CFCs Refrigerants:

HCFCs Refrigerants

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Molina and Rowlands findings were published in 1974 and shocked the entire world.

Their findings were later confirmed by scientists around the world, especially the British Antarctic Survey in 1986. This led to the Montreal Protocol of 1987 that banned CFCs around the world. They received the Nobel Prize for Chemistry in 1995.

25

6. Montreal Protocol
The Montreal Protocol on Substances that Deplete the Ozone Layer is an international treaty designed to protect the ozone layer by phasing out the production of numerous substances believed to be responsible for ozone depletion. The treaty was opened for signature on September 16, 1987. Article A 5 (1) : Special situation of developing countries Any Party that is a developing country and whose annual calculated level of consumption of the controlled substances in Annex A is less than 0.3 kilograms per capita on the date of the entry into force of the Protocol for it.

26

27

Hole in Ozone Layer

The concentration of ozone in the atmosphere is measured in "Dobson Units", the average concentration of ozone in the atmosphere is about 300 Dobson Units. The ozone hole is considered to be wherever the concentration drops below 220 Dobson Units.

28

29

Velders et al., PNAS, 2007

30

31

7. What is GWP?
Global warming potential (GWP) is a measure of how much a given mass of greenhouse gas is estimated to contribute to global warming. It is a relative scale that compares a gas to that of the same mass of CO2 (GWP of CO2 is by definition 1). Chemical formula CO2 CH4 N2O CHF3 CH2F2 CH3F C2HF5 C2H2F4 CH2FCF3
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Species CO2 Methane Nitrous oxide HFC-23 HFC-32 HFC-41 HFC-125 HFC-134 HFC-134a

Lifetime (years) variable 12 120 264 5.6 3.7 32.6 10.6 14.6

Global Warming Potential (100 Years) 1 21 310 11700 650 150 2800 1000 1430

Ref : Calm JM, 2008 33

8. Total equivalent warming impact (TEWI)

TEWI

= GWP (direct; refrigerant leaks incl. EOL) + GWP (indirect; operation) = (GWP x m x L annual x n) + (GWP x m x (1- recovery)) + (E annual x x n)

Where: GWP = Global Warming Potential of refrigerant, relative to CO2 (GWP CO2 = 1) L annual = Leakage rate p.a. (Units: kg) n = System operating life (Units: years) m = Refrigerant charge (Units: kg) recovery = Recovery/recycling factor from 0 to 1 E annual = Energy consumption per year (Units: kWh p.a.) = Indirect emission factor (Units: kg CO2 per kWh)

34

9. Kyoto Protocol
The Kyoto Protocol is a protocol to the United Nations Framework Convention on Climate Change (UNFCCC), Kyoto, Japan, on 11 December 1997 that set binding obligations on the industrialized countries to reduce their emissions of greenhouse gases.

Ref : Calm JM, 2008 35

Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007

36

CO2 emissions

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2eq/yr 5-6 times Kyoto target (incl. offsets: HFCs, ozone depl.)

Velders et al., PNAS, 2007

37

Regional Shares of World Carbon Emissions, 1997 & 2020

Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007

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10. Fourth generation Refrigerants

HFO-R1234yf CH2=CF-CF3
Vapor Pressure Vs. Temperature
3.5 3.0

HFO-R1234ze CHF=CH-CF3
Vapor Pressure Vs. Temperature
3.5 3.0

Pressure, MPa

134a
2.5 2.0 1.5 1.0 0.5 0.0 -20 0 20 40 60 80 100

Pressure, MPa

2.5 2.0 1.5 1.0 0.5 0.0 -20

1234ze(E) 134a

1234yf

20

40

60

80

100

Environmental ODP = 0 GWP100 = 4 Atmospheric Life: 11 days

Temperature, oC

Environmental ODP = 0 GWP100 = 6 Atmospheric Life: 18 days

Temperature, oC

39

10. Fourth generation Refrigerants

40

10. Fourth generation Refrigerants

41

Ref: NIST Chemistry WebBook

11. Retrofit options

The Example of Room A/C
Propane (R290) Refrigerant price Cost for performance Compressor, EX, etc. Cost for safety Charge reduction Joint Electronic parts Leak detector Ventilation Cost for handling Manufacture Supply chain Installation Service Disposal Cheap Modification required Same as R22 R32 Cheap Near as R410A Same as R410A HFO1234yf Expensive Larger comp. Larger pipe etc.

Component which increases cost

CO2(R744) Cheap Two-stage comp. High-pressure etc.

Important (ex.230g) Special joint Sealing etc. Necessary Necessary

Necessary Special joint -

Necessary Special joint -

Necessary -

Special facility Qualification Qualified person Qualified person Qualification

Modified facility Modification Modification Modification Modification

Modified facility Modification Modification Modification Modification

Modified facility Qualification Qualified person Qualified person

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ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Benefits of R1234yf: 1. GWP=4.0 ( & ODP=0.0) 2. Very low atmospheric life 3. Low TEWI 4. Complying to European Norms 5. Complying to US Norms

R1234yf Implementation issues: 1) Performance impact 2) Additional part (IHX) to match the performance 3) Availability 4) Cost impact 5) Retro fitment issues (New oil type, New ports) 6) Mild Flammability

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications

TXV

Additional part

Compressor

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications

S.No. 1 2

Refrigerant R134a R1234yf

Additional Cooling Sub-cool by Capacity, W IHX 0 0 5485.8 5026.4 -8.4%

Power Consumption, W 2185 2136 -2.2% 2151 -1.6% 2163 -1.0% 2173 -0.5% 2181 -0.2%

COP 2.511 2.353 -6.3% 2.422 -3.5% 2.489 -0.9% 2.552 1.6% 2.613 4.1%

Quality of refrigerant at TXV outlet 0.377 0.477 10% 0.4 2%

R1234yf

5210.6 -5.0%

Te=0.3 C
4 R1234yf 10 5382.9 -1.9% 5 R1234yf 15 5545 1.1% 6 R1234yf 20 5698.6 3.9% 0.354 -2% 0.309 -7% 0.265 -11%

Tc=57.7 C SC=5 C SH=10 C i=70% v=65% Vs=138.3 cc N=2000 rpm

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications No IHX X=0.377

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications No IHX X=0.447

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 5 C additional sub-cool X=0.400

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 10 C additional sub-cool X=0.354

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 15 C additional sub-cool X=0.309

ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 20 C additional sub-cool X=0.265

Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications
Objective Changeover of refrigerant types R134a to R1234yf
As per Montreal Protocol (1987), the changeover happened from R12 to R134a to avoid the ozone layer depletion. Kyoto Protocol (1997) has set the target to reduce the emissions of greenhouse gases, which are contributing the global warming. EU Directives for MAC (2009) have set the target to use the refrigerants having GWP < 150 for Automotive Air Conditioning Applications.
Refrigerant type CFC HCFC HFC HFO Natural ref. Grade R12 R22 R134a R1234yf CO2 ODP 1 0.055 0 0 0 GWP 10900 1810 1430 4 1 Cost of ownership low 2nd Generation low low slight high 4th Generation very high 3rd Generation Development

1 2

1 Changeover as per Montreal Protocol 2 Changeover due to Kyoto Protocol and EU MAC Directives, US EPA Rules.

12. Reefer Truck Classification

A]
Application

ACMA AWARDS 2009-10

Frozen (upto -25 C)

Chilled (upto 0 C)

Fresh (upto 10 C)

B]

Drive

Direct Drive

Auxillary engine driven (cabin volume > 22 m3)

With standby unit

Without standby Unit

ACMA AWARDS 2009-10

Refrigeration System

Refrigerant : Frozen application: R404a Chilled & Fresh application : R404a/R134a

Operating Conditions(frozen): Condensing side: 28~32 bar Evaporating side: 1.5~2.5 bar Hot gas Defrost Hot gas bypass from compressor out to evap in for defrosting operation

Why R404a for Freezing application?

ACMA AWARDS 2009-10

Why R404a for Freezing application?

ACMA AWARDS 2009-10

Refrigerant Number R404A R125 R143a R134a R410A R32 R125

Compounds R125/143a/134a Pure Pure Pure R-32/125 Pure Pure

Composition (Weight %) 44/52/4 44% 52% 4% 50/50 50% 50%

ODP 0 0 0 0 0 0 0

GWP 3700 3420 4180 1430 2100 716 3420 1505 2174 57 358 1710

Why R404a for Freezing application?

ACMA AWARDS 2009-10

Why R404a for Freezing application?

Saturation Pressure vs Temperature of Refrigerants

ACMA AWARDS 2009-10

41 36
Saturation Pressure, Bar(a)

R134a

R404a

31 26 21 16 11 6 1 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110

Saturation Temperature, C

Why not R410a for Freezing application?

ACMA AWARDS 2009-10

ACMA AWARDS 2009-10 Performance Testing

1. Cooldown Test -25 C has to be achieved at an ambient of 45 C within 6.5 hours 2. Retention Test Ambient temp: 35 C Time taken from -25 C to 0 C : 2 hrs +/- 15 mins Time taken from 0C to 15C : 3.0 hrs +/- 15 mins 3. Air Tightness Test A pressure of 250 +/- 10 pa above atmospheric is maintained inside the chamber & air flow required to maintain this internal pressure is recorded. The air leakage rate should not be more than 5 m3/h 4. Heat Leakage Test K = Q/A(Ti To) K = Heat leakage (W/m2/C). Q = Electrical power dissipated by heater and fans, A = Mean s/c area, Ti = Mean inside temperature, To = Mean outside temperature. 5. Rain Test Test should be conducted as per IS-11865-2006. No water leakage inside the cabin should be detected after the test.

International Standards
Reefer Truck Test Conditions with R404a Standard/ Condenser In Evaporator In Specificatio Temperature Temperature Compressor S.No. n of air of air Speed 1 Australian Standard No. AS:4982-2003 2.1 +38 C +12 C 1500 rpm 2.2 +38 C 0C 1500 rpm 2.3 +38 C -18 C 1500 rpm 2.4 +38 C -28 C 1500 rpm 2 Japanese Standard No. JRA_4045:2008 3.1 +35 C +10 C 1800 rpm 3.2 +35 C 0C 1800 rpm 3.3 +35 C -18 C 1800 rpm

ACMA AWARDS 2009-10

Duration in Cool Down test <= 6.5 Hr <= 6.5 Hr <= 6.5 Hr <= 6.5 Hr

ACMA AWARDS 2009-10

Performance

45 40 35 30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30 0

+45 C ambient Engine :2000 rpm Ram air : 40 kmph

+45 C ambient Engine :Idle rpm Ram air : No

+35 C ambient Engine :Idle rpm Ram air : No

Avg. Cabin Temp., C

Controller tripped the compressor after the set point of -25 C is reached

Cool Down -17.2 C reached Cool Down -22.4 C reached

60

120

180

240 Time, min

300

360

420

480

AWARDS of 2009-10 13. Future ACMA technology Air-Conditioning System

TIFFE Approach

Dual loop air conditioning Development of innovative heat exchangers Use of innovative coolants

ACMA AWARDS 2009-10 Future technology of Air-Conditioning Single loop Conventional Circuit System

ACMA AWARDS 2009-10 Future technology of Air-Conditioning CRU: Compact Refrigeration Unit System

TIFFE Approach

14. Conclusion
Thomas Midgley (1928) had invented the CFCs & HCFCs, but the large use of these refrigerants had created severe threat to the earth in terms of ozone layer depletion and global warming (HFCs). McNeill has stated that Midgley "had more impact on the atmosphere than any other single organism in Earth's history. Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants. PLAN DO
66

CHECK

ACT

15. References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. ASHRAE, 2007, https://osr.ashrae.org/Public%20Review%20Draft%20Standards%20Lib/34z2007%201st%20PPR%20Draft.pdf ASHRAE, 2008, http://www.ashrae.org/File%20Library/docLib/Public/20080807_34m_thru_34v_final. pdf Anant et al. Investigation of Cubic EOS models for HFO-1234yf Refrigerant Used in Automotive Application, International Refrigeration and Air Conditioning Conference at Purdue, July 16-19, 2012 Bjrn Palm, REFRIGERANTS OF THE FUTURE, 10thIEA Heat Pump Conference 2011, 16 - 19 May 2011, Tokyo, Japan http://kth.diva-portal.org/smash/get/diva2:483181/FULLTEXT01 Calm JM, Composition Designations for Refrigerants, ASHRAE Journal, November 1989 Calm JM, Global Warming Impacts of Chillers, Heating Piping Air Conditioning, February 1993 Calm JM, Refrigerant Safety, ASHRAE Journal, 1994 Calm JM, The next generation of refrigerants - Historical review, considerations, and outlook, Int. J. Refrig. 31 (7), 1123-1133 (2008). http://dx.doi.org/10.1016/j.ijrefrig.2008.01.013 Calm JM, Refrigerant Transitions ... Again. ASHRAE-NIST Refrigerants Conference 2012 Carmen J. Giunta THOMAS MIDGLEY, JR., AND THE INVENTION OF CHLOROFLUOROCARBON REFRIGERANTS: IT AINT NECESSARILY SO , Bull. Hist. Chem., VOLUME 31, Number 2 (2006 CHARLES F. KETTERING , BIOGRAPHICAL MEMOIR of THOMAS MIDGLEY, JR. 18891944, PRHSENTED TO THE ACADEMY AT THE ANNUAL MEETING, 1947. Dylan S. Cousins and Arno Laesecke, Sealed Gravitational Capillary Viscometry of Dimethyl Ether and Two Next-Generation Alternative Refrigerants Journal of Research of the National Institute of Standards and Technology, Volume 117 http://dx.doi.org/10.6028/jres.117.014 , 2012 G Venkatarathnam and S Srinivasa Murthy, Refrigerants for Vapour Compression Refrigeration Systems, RESONANCE February 2012 GUIDE 2012: Natural Refrigerants Market Growth for Europe, shecco publications Imke et al. Energy consumption of battery cooling in electric hybrid vehicles, International Refrigeration and Air Conditioning Conference at Purdue, July 16-19, 2012 67

13. 14. 15.

Continuing .

16. NASA, 2007, http://www.nasa.gov/vision/earth/environment/ozone_recovering.html Date: March11, 2011 17. NIST Standard Reference Database 23, REFPROP - Thermo dynamic properties of refrigerants and refrigerant mixtures, Version 3.04, NIST, USA, 1991. 18. M. Richter, M. O. McLinden, and E. W. Lemmon, Thermodynamic Properties of 2,3,3,3Tetrafluoroprop-1-ene (R1234yf): Vapor Pressure and pT Measurements and an Equation of State, J. Chem. Eng. Data 56 (7), 3254-3264 (2011). http://dx.doi.org/10.1021/je200369m 19. M. O. McLinden, M. Thol, and E. W. Lemmon, "Thermodynamic Properties of trans-1,3,3,3tetrafluoropropene [R1234ze(E)]: Measurements of Density and Vapor Pressure and a Comprehensive Equation of State", Proceedings of the 2010 International Refrigeration and Air Conditioning Conference, Purdue, West Lafayette, IN, USA, Paper No. 2189. http://docs.lib.purdue.edu/iracc/1041/ 20. Handbook for the Montreal Protocol on Substances that Deplete the Ozone Layer, Ninth edition (2012), United Nations Environment Programme. 21. The Montreal Protocol and the Green Economy, 2012, UNEP. 22. THE AUSTRALIAN INSTITUTE OF 23. METHODS OF CALCULATING TOTAL EQUIVALENT WARMING IMPACT (TEWI), AIRAH, Best Practise Guidelines, 2012, 24. KYOTO PROTOCOL TO THE UNITED NATIONS FRAMEWORK CONVENTION ON CLIMATE CHANGE, 1998, UN. 25. Reasor, Pamela; Aute, Vikrant; and Radermacher, Reinhard, "Refrigerant R1234yf Performance Comparison Investigation" (2010). International Refrigeration and Air Conditioning Conference. Paper 1085 http://docs.lib.purdue.edu/iracc/1085/ 26. R1234yf.fld - NIST, www.boulder.nist.gov/div838/theory/refprop/R1234YF.FLD 27. R1234ze.fld - NIST , www.boulder.nist.gov/div838/theory/refprop/R1234ZE.FLD 28. SAE, 2010a, http://www.sae.org/mags/aei/8702 , Date: April 22, 2011. 29. SAE, 2010b, http://www.sae.org/mags/AEI/8074 , Date: April 22, 2011. 30. SAE, 2011, http://www.sae.org/standardsdev/tsb/cooperative/altrefrig.htm , Date: April 22, 2011 68

Continuing .

31. http://www.reefercargocare.com/refrigerants.html 32. http://www.reefercargocare.com/ozone-depleting-substances.html 33. http://www.lindegas.com/en/products_and_supply/refrigerants/fluorine_refrigerants/hfo_refrigerants.html 34. http://humantouchofchemistry.com/frank-rowland-and-mario-molina.htm 35. http://www.beyonddiscovery.org/content/view.page.asp?I=89 Inventor : Thomas Midgley US Patent No. 2013062

No.

dated

patent Title Preparation of aliphatic halofluoro compounds Manufacture of halo-fluoro derivative of aliphatic hydrocarbons Heat transfer and refrigeration Manufacture of antimony trifluoride Fluorination process 69

filed as on Feb. 26, 1931 Feb. 24, 1931 Nov.19, 1931 June 30, 1934 May 7, 1938

Sep.3, 1935

2 3 4 5

2007208 2104882 2024008 2192143

July 9,1935 Jan.11, 1938 Dec.10, 1935 Feb.27, 1940

70