Buffalo, NY 14210 

716-827-6200 

Manager of Standards 

ASH RAE 

1791 Tullie Circle NE 

Atlanta, GA 30329-2305 

December 12, 2013 

Re: ASHRAE Standard 34 Refrigerant Designation and Safety Classification 

Application for R-134a/R-1234ze(E) (42.0/58.0% by mass) 

Dear Sirs; Please find herewith supporting data and required certifications for Honeywell's 

application to ASH RAE SSPC 34 for assignment of a number designation and safety 

classification for R-134a/R-1234ze(E) (42.0/58.0% by mass). We request this 

application for submission and consideration at the scheduled January, 2014 meeting 

in New York, New York. 

Enclosed are 2 bound copies of our application for administrative use. An electronic 

version will be e-mailed separately. 

Sincerely yours, 

Mark W. Spatz 

Global Leader Refrigerant Technology- Honeywell Refrigerants 
Submission to ASHRAE SSPC 34 Committee 

December 12, 2013 

Request for Refrigerant Designation and Safety Classification 

For 

R-134a/R-1234ze(E) (42.0/58.0% by mass) 

PRIMARY CONTACT 

Mr. Mark W. Spatz 

Global Leader Refrigerant Technology 

Honeywell Fluorine Products 

-1 -
Section 1 -Administrative Information 3 

Section 2- Designation Information 7 

Section 3- Toxicity Data 10 

Section 4- Flammability Information 29 

Section 5- RCL Value I Contaminants and Impurities 53 

Section 6 - Appendices 55 

. 2. 
Section 1: Administrative Information 

- 3-
Address: 

Primary Contact: 

Address: 

Telephone: 

FAX: 

Email: 

Other Contacts: 

Address: 

Telephone: 

FAX: 

Email: 

Honeywell International Inc. 

Specialty Materials 

101 Columbia Road 

Morristown, NJ 07962 

Mr. Mark W. Spatz 

Global Leader Refrigerant Technology 

Honeywell Fluorine Products 

Buffalo Research Laboratory 

20 Peabody Street 

Buffalo, NY 1421 0 

(716) 827-6238 (716) 827-6275 

mark.spatz@honeywell.com 

George Koutsaftes 

Business Director 

Honeywell Specialty Materials - Refrigerants 

101 Columbia Road 

Morristown, NJ 07962 

(973) 455-2996 (973) 455-6394 

george.koutsaftes@honeywell.com 

Applicant's Interest: Honeywell Fluorine Products Division desires to manufacture 

and sell the subject blend as a refrigerant for refrigeration and air-conditioning 

applications. 
classification of toxicity or flammability safety is being withheld. 1/We further certify that we 

have reviewed ANSI/ASH RAE Standard 34-2010 (including all published addenda thereto) 

and that the information provided in this application is consistent with the requirements of that 

standard. ~~4 Mark W. Spatz George Koutsaftes 

Global Leader Refrigerant Technology Business Director 

Honeywell Specialty Materials Honeywell Specialty Materials - Refrigerants 

Primary Contact Alternate Contact 

-5-
We understand that designations and safety classifications recommended for public review 

approval or publication are not assigned and may be revised or disapproved 

Until actually published in an addendum or revision to Standard 34. 

Mark W. Spatz George Koutsaftes 

Global Leader Refrigerant Technology Business Director 

Honeywell Specialty Materials Honeywell Specialty Materials - Refrigerants 

Primary Contact Alternate Contact 

• 6-
Section 2: Designation Information 

-7-
Honeywell Fluorine Products Division, manufacturer, submits this application to ASHRAE under ANSI/ASHRAE 

Standard 34-2010 (including published addenda) for assignment of a Refrigerant Designation and Safety 

Classification for our zeotropic refrigerant blend of R-134a/R-1234ze(E) (42.0/58.0% by mass), as defined under 

Designation Information of this application. This refrigerant blend has been developed as a lower global warming 

replacement for Refrigerant R-134a. 

Refrigerant Identification - Section 9.5.1 

The refrigerant blend is formulated with the following components (in order of increasing boiling 

points): 

R-134af/R-1234ze(E) (42.0/58.0% by mass)(+/- 2.0/±2.0% by mass) 

The refrigerant components of the zeotropic blend as defined above are described as: 

Chemical Name Chemical Formula CAS No. 

R-134a 1,1, 1 ,2-Tetrafluoroethane 

R-1234ze(E) Trans-1,3,3,3-Tetrafluoro-1-propene CHFCHCF3 29118-24-9 

t 

Properties of Individual Components- ASH RAE Sandard 34-2010 Section 9.5.2.1 

Molecular Mass, g/mole 

Normal Boiling Point at 101.3 kPa, oc 

Saturated Vapor Pressure at 20°C, kPa Saturated Vapor Pressure at 60°C, kPa 

Temperature at the Critical Point, oc 

Pressure at the Critical Point, kPa 

Specific Volume at the Critical Point, m3/kg 

Uses and Typical Application 

Temperatures: 

Evaporating temperatures in the range but 

not necessarily limited to that range. 

Condensing temperatures in the range but 

not necessarily limited to that range. 

R-134a 

102.0 

-26.1 

572 

1682 

101.1 

4059 

0.00195 

Domestic 

and 

commercial 

refrigeration; 

as a blend 

component of 

R-407C, 

R-404A, 

and the like. 

-8-

R-1234ze(E) 

114.0 

-19.0 

427 

1277 109.4 

3636 0.00204 

Air conditioning and 

refrigeration; 

as a blend 

component. 
Bubble Point at 101 kPa 

Dew Point at 101 kPa 

Maximum Temperature Glide 

At Normal Boiling Point At 20°C 

Latent Heat of Vaporization at 60°C 

Specific Heat Ratio of Vapor at 60°C 

Temperature at Critical Point 

Pressure at the Critical Point, kPa 

Specific Volume at the Critical Point 

Mole basis and Mass basis 

Uses 

The subject refrigerant blend is 

proposed for applications historically 

served by R-134a in vapor 

compression systems. 

Typical Application Temperatures 

Evaporating temperatures in the range 

of -40°C to +1 ooc 

but not necessarily limited to that range. 

Condensing temperatures in the range 

of +15°C to +65°C 

but not necessarily limited to that range. 

Proposed Composition Tolerances for 

Classification 

-23.4°C 

-22.8°C 

0.6°C 0.6°C 

135.2 kJ/kg 1.36 104.4°C 

3819 

R-134a (1,1,1,2-Tetrafluoroethane) ±2.0% by mass 

Nominal 42.0 % by mass 

R-1234ze(E) (trans-1,3,3,3- ±2.0% by mass 

Tetrafluoroprop-1-ene) Nominal 58.0% 

by mass 

Worst Case Formulation (WCF) R-134a/R-1234ze(E) (40.0/60.0% by mass) Worst Case Fractionation Formulation Final liquid composition, -13.2C, vapor leak from a cylinder at 

90% of maximum allowed DOT fill. R-134a/R-1234ze(E) 

(17.3/82.7% by mass) 

Refrigerant Blend Critical Temperature and Critical Pressure- ASHRAE Standard 34 Section 9.5.2.5 

Critical Temperature: 104.4°C 

Critical Pressure: 3819 kPa 

Critical Specific Volume: 0.00203 m3/kg 

-9-
Section 3: Toxicity Information 

-10-
Toxicity Information HFC-134a 

Acute Toxicity 

a. ACGIH TLV-c: None assigned 

b. ACGIH TLV-STEL: None assigned 

c. NIOSH IDLH: None assigned 

d. 4-hr ALC rat= > 359,300 ppm (v/v)<5> e. LD50: > 359,300 ppm<5> 

f. Cardiac sensitization: The No Observed Effect Level for epinephrine challenged dogs is 50,000 ppm (v/v) 

and the Lowest Observed Effect Level is 75,000ppm (v/v).(7) 

g. Anesthetic and central nervous system effects: EC50 270,000 ppm.<6> 

h. Other escape-impairing effects and permanent injury: None reported. 

ANIMAL TOXICITY DATA 

A. Acute Toxicity and Irritancy 

A. Acute Toxicity and Irritancy 

1. Oral 

Substance is a gas and has not been tested for oral toxicity. 

2. Eye Irritation 

Substance is a gas and in a specialized study for eye irritation where it was sprayed into the 

eye of a rabbit for 5 or 15 seconds, it was found to be very slightly irritating. It is not 

possible to determine if the irritation was from potential freezing associated with the 

evaporation of the test substance or some other property of the substance. However, in a 4-

week and a 13 week inhalation toxicity study with exposures up to 5% in air, 6-hours/day, 5 

days/week, no signs of irritation were seen.111 

3. Skin Absorption 

No data 

4. Skin Irritation 

Substance is a gas and in a specialized study for skin irritation where 0.5 ml was applied to a 

square of 8 gauze pads, it was found to be very slightly irritating. It is not possible to determine 

-11 -
Following a single injection of Freund

s complete adjuvant, guinea pigs were treated with 7 

applications of 0.5 ml of HFC-134a applied to gauze pads on their backs. Treatments were 

separated by 2-3 days. After a period of 12 days, the guinea pigs were challenged with an 8th 

application of 0.5 ml of HFC-134a. There was no evidence of sensitization.131 

6. Inhalation Toxicity 

a. An approximate lethal concentration for a 4-hour exposure, the lowest concentration that 

produced death, was 567,000 ppm. In this study, mortalities were 0/6 at 81,100, 205,200 and 

359,300 ppm, 5/6 at 566,700 ppm, 0/6 at 646,700 ppm and 2/6 at 652,700 ppm. The range of 

concentrations in the 566,700 exposure level group was 494,400 to 668,800 ppm and thus 

overlapped with the higher exposures. Most rats showed signs of decreased activity and 

dyspnea, salivation and lachrymation during the HFC-134a exposure. Since the higher 

exposure levels overlapped, the best estimate for the LC50 was taken as > 359,300 ppm.141 

b. In an undocumented study, Collins reported that the 4-hr LC50 for exposure to HFC-134a 

was> 500,000 ppm and the 15 minute LC50 was> 800,000 ppm.151 

c. HFC-134a was not lethal to dogs exposed to a level of 700,000 or 800,000 ppm for 3 to 5 

hours.151 

d. A 10 minute ECso for anesthetic effects, measured by loss of the righting reflex, was 

280,000 ppm in the rat and 270,000 ppm in the mouse.161 

e. In this study a group of 8 beagle dogs were exposed to levels of 50,000, 75,000 and 

100,000 ppm of HFC-134a. Initially a determination was made for the maximum level of 

epinephrine that would not cause a cardiac arrhythmia. The dogs were then exposed to the 

test compound for a total of 10 minutes. After the first five minutes of exposure, each dog 

received an injection of epinephrine at the pre-determined maximum sub-arrhythmia dose. 

During the next five minutes of exposure, the dogs were monitored for the development of a 

cardiac arrhythmia. There were no arrhythmias, nor other signs of toxicity seen in the dogs 

exposed to 50,000 ppm. Exposure of dogs to levels of 75,000 ppm and 100,000 ppm of HFC134a resulted in arrhythmias. It was concluded that exposure to 75,000 ppm represented the 

threshold for cardiac sensitization.(7) 

-12. 
monitored for the development of a cardiac arrhythmia. There were no arrhythmias, nor 

other signs of toxicity seen in the dogs exposed to 40,000 ppm. Exposure of dogs to levels 

of 80,000 ppm and above of HFC-134a resulted in arrhythmias. It was concluded that 

exposure to 80,000 ppm represented the threshold for cardiac sensitization. 181 

B. Repeat Exposure Toxicity Data 

a. Subacute Toxicity 

In this GLP study groups of 16 male and 16 female Alpk/APfSD Wistar-derived rats were 

exposed, whole body, to vapors of HFC-134a at levels of 0 (control), 1,000, 10,000 or 50,000 ppm 

6-hours/day, 5 days/week for 4 weeks. There were no observations of clinical abnormalities, nor 

adverse effects on body weight gain, food consumption, nor treatment related changes in WBC 

parameters. There were no adverse findings in the analysis of organ weights, or macroscopic or 

microscopic examination of tissues, including a complete examination of tissues from the 

respiratory tract Overall, it can be concluded that the No-Adverse-Effect-Level (NOAEL) for a 4-

week exposure to HFC-134a was at least 50,000 ppm.191 

b. Subchronic Toxicity 

In this GLP study groups of 20 male and 20 female Alpk/APfSD Wistar-derived rats were 

exposed, whole body, to vapors of HFC-134a at levels of 0 (control), 2,000, 10,000 or 50,000 ppm 

6-hours/day, 5 days/week for 13 weeks. There were no observations of clinical abnormalities, or 

adverse effects on body weight gain, food consumption, nor treatment related changes in WBC 

parameters. There were no adverse findings in the analysis of organ weights, or macroscopic or 

microscopic examination of tissues, including a complete examination of tissues from the 

respiratory tract. Overall, it can be concluded that the No-Adverse-Effect-Level (NOAEL) for a 

13-week exposure to HFC-134a was at least 50,000 ppm.1101 

c. Chronic Toxicity/Carcinogenicity 

In this GLP study groups of 85 male and 85 female Alpk/APfSD Wistar-derived rats were 

exposed, whole body, to vapors of HFC-134a at levels of 0 (control), 2,500, 10,000 or 50,000 ppm 

6-hours/day, 5 days/week for 104 weeks. There were no observations of clinical abnormalities, 

-13-
Observed-Adverse-Effect-Level (NOAEL) for the chronic study with HFC-134a was 10,000 ppm.1111 

d. Reproductive/Developmental Toxicity 

In this GLP study groups of 29-30 pregnant Alpk/APfSD Wistar-derived rats were exposed, 

whole body to vapors of HFC-134a at levels of 0 (control), 1 ,000, 10,000 or 50,000 ppm 6-

hours/day, 7 days/week during days 6-15 of gestation. There were no differences in the 

incidence of the number of implantation sites, pre- and post implantation losses, live and dead 

fetuses, resorptions, or ratio of males to females between the groups. Skeletal ossification was 

slightly delayed at 50,000 ppm. It was concluded that HFC-134a is neither teratogenic nor 

embryotoxic at exposure levels up to 50,000 ppm, but at the highest level HFC-134a may be 

slightly fetotoxic. The clear NOEL for this study was 10,000 ppm.'12' 

A GLP study was conducted using groups of 28 pregnant New Zealand white rabbits exposed to 

levels of 0 (control), 2,500, 10,000 and 40,000 ppm. Again the exposures were 6-hrs/day, from 

days 7-19 of gestation. The exposures at 10,000 and 40,000 ppm resulted in slightly retarded 

body weight gains and decreased food consumption. No significant effects were seen in the 

pups from any exposure group. It was concluded that the no-observed-effect-level for maternal 

toxicity was at least 2,500 ppm and for the pups it was 40,000 ppm. 1131 

In a GLP study conducted to support the development of HFC-134a for use in medical inhalers, 

HFA-134a was administered to AHA rats by snout-only inhalation exposure for 1 hour/day at 

levels up to 50,000 ppm, throughout gametogenesis (sexual development), mating, pregnancy 

and lactation. The only treatment related effect was a slight reduction in body weight gain seen 

in the male rats in the 50,000 ppm exposure level group. Exposure to HFA-134a did not cause 

and effects in reproductive performance, development of maturation during two successive 

generations.1141 

e. Mutagenicity 

A GLP Ames assay was conducted with HFC-134a which involved exposure of bacterial cells TA 

1535, TA1537, TA 98, TA 100, and WP2 uvrA both with and without S-9 metabolic activation. 

-14-
HFC-134a was not active (not clastogenic) in this assay. 

In the GLP micronucleus study, NMRI mice received a single exposure by inhalation to 50,000, 

150,000 and 500,000 ppm. Bone marrow cells were collected and analyzed for the presence of 

micronuclei. Under the conditions of this assay HFC-134a did not produce chromosomal 

damage or damage to the mitotic spindle apparatus in bone marrow cells. 1171 

The clastogenic potential of HFC-134a was investigated using a Chinese hamster lung cell line. 

This GLP study used exposures up to 100% for 24 and 48 hours without metabolic activation or 

for 6 hours with metabolic activation. When compared to the negative control, there was no 

increase in the incidence of chromosomal aberrations.1181 

RECOMMENDED WEEL GUIDE 

A WEEL OEL has been approved by the WEEL Committee for HFC-134a. It recommends 1,000 ppm 

as an 8-hour TWA. 1191 

MATERIAL SAFETY DATA SHEET 

A Honeywell Material Safety Data sheet for Genetron® 134a is attached.1201 

RECOMMENDED ATEL for HFC-134a 

LC50 >359,000PPM 

Cardiac sensitization NOEL = 50,000 ppm 

Anesthetic/CNS effect EC50 = 270,000 ppm 

ATEL: 50,000 ppm 

REFERENCES 

(1) Mercier 0. 1990a. HFA-134a: Test to evaluate the ocular irritation in the rabbit. Unpublished 

report 912349. Hazleton, Lyon, France. Atochem, Paris, France. 

(2) Mercier 0. 1989. HFA-134a: Test to determine the index of primary cutaneous irritation in the 

rabbit. Unpublished report 911422. Hazleton, Lyon, France. Atochem, Paris, France. 

-15-
422-79. Haskell laboratory for Toxicology and Industrial Medicine. Du Pont de Nemours, 

Newark, DE, USA. 

(5) Collins MA.1990. Klea 134a: Acute inhalation data. Personal communication.ICI Chemicals & 

Polymers, Runcorn, Cheshire, UK. 

(6) Shulman M, Sadove MS. 1967. 1,1,1,2-Tetrafluoroethane: An inhalation anesthetic agent of 

intermediate potency. Anesth Anatg Current Researches 46:629-633. 

(7) Mullin LS. 1979. FC 134a: Cardiac sensitization. Unpublished report 42-79. Haskell Laboratory 

for Toxicology and Industrial medicine. Du Pont de Nemours, Newark, DE, USA. 

(8) Hardy CJ, Sharman IJ, Clark GC. 1991. Assessment of cardiac sensitization in dogs: 

Comparison of HFA134a and A12. Unpublished report CTUC/2521. ICI Central Toxicology 

Laboratory, Alderley Park, Macclesfield, Cheshire, UK. 

(9) Riley RA, Bennett IP, Chart IS, Gore CW, Robinson M, Weight TM. 1979. Arcton 134a: Subacute 

toxicity to the rat by inhalation. Unpublished report CTUP/463. ICI Central Toxicology 

Laboratory, Alderley Park, Macclesfield, Cheshire, UK. 

(10)Hext PM. 1989. 90-Day inhalation toxicity study in the rat. Unpublished report CTUP/2466.1CI, 

Central Toxicology laboratory, Alderley Park, Macclesfield, Cheshire, UK. 

(11)Hext PM, Parr-Dobrzanski RJ.1993. HFC-134a: 2-Year inhalation toxicity study in the rat. 

Unpublished report CTUP/3841. Zeneca, Central Toxicology Laboratory, Alderley Park, 

Macclesfield, Cheshire, UK. 

(12)Hodge MCE, Kilmartin M, Riley RA, Weight TM, Wilson J. 1980. Arcton 134a: Teratogenicity study 

in the rat. ICI, Central Toxicology Laboratory, Alderley Park, Macclesfield, Cheshire, UK. 

-16-
and maturation of rats. Human and Experimental Toxicol. 15, 508-517 (1996). 

(15)Araki A. 1991. Report on reverse mutation assay in bacteria on tetrafluoroethane. Unpublished 

report study 5292, 5312. Japan Bioassay Laboratory, Japan Industrial Safety and Health 

Association, Hirasawa, Hadano-shi, Japan. 

(16)Mackay JM. 1990. HFC-134a: An evaluation in the in vitro cytogenetic assay in human 

lymphocytes. Unpublished report CTUP/2977. ICI, Central Toxicology Laboratory, Alderley Park, 

Macclesfield, Cheshire, UK. 

(17)Muller W, Hofmann T. 1989. CFC 134a: Micronucleus test in male and female NMRI mice after 

Inhalation. Unpublished report study 88.1244. Pharma Research Toxicology and pathology. 

Hoechst, Frankfurt, Germany. 

(18)Askura M.1991. Report on a chromosomal aberration test of 1,1,1,2-tetrafluoroethane in cultured 

mammalian cells. Unpublished report study 5879. Japan Bioassay Laboratory, Japan Industrial 

Safety and Health Association, Hirasawa, Hadano-shi, Japan. 

(19)AIHA. 1991. 1,1,1,2-Tetrafluoroethane. Workplace environmental exposure level guide. 

American Industrial Hygiene Association, Fairfax, VA, USA. 

(20)Honeywell (December 6, 2012). Genetron® 134a Material Safety Data Sheet, Honeywell 

International, Inc., 101 Columbia Road, Morristown, NJ, USA. 

-17-
a. ACGIH TLV if assigned: None 

b. ACGIH TLV-STEL if assigned: Neither ACGIH nor AIHA recommend ceiling or short 

term exposure limits for HF0-1234ze(E). 

c. NIOSH IDLH if assigned: NIOSH has not assigned an IDLH for HF0-1234ze(E). 

d. 4-hr LC50 rat >207,000 ppm (v/v)15> 

e. LD50 if available: Not applicable to gases 

f. Cardiac sensitization NOEL: >120,000 ppm (v/v)16> 

g. Anesthetic and central nervous system effects: NOAEL >207,000 ppm (v/v). 15> 

Rats that were exposed to vapors of HF0-1234ze(E) at levels up to 207,000 ppm for 4 

hours showed no evidence of anesthetic or CNS effects15>. 

h. Other escape-impairing effects: None have been identified. 

ANIMAL TOXICITY OAT A 

A. Acute Toxicity and Irritancy 

1. Oral 

Substance is a gas and has not been tested for oral toxicity. 

2. Eye Irritation 

The substance is a gas and has not been tested for eye irritation. However, 

in 2-week, 4-week and 13-week inhalation toxicity studies with exposures up 

to 5%, 1.5% and 1.5% in air, respectively, 6-hours/day, 5 days/week, no 

signs of ocular irritation were seen:11 •2•3> 

3. Skin Absorption 

Substance is a gas and has not been tested for skin absorption toxicity. 

4. Skin Irritation 

The dermal irritation of HF0-1234ze(E) was evaluated in a GLP study in albino 

rabbits following OECD guideline 404: Acute Dermal Irritation/Corrosion. 

Initially, 0.4 ml of test substance was applied to the back of one rabbit via a 

hill top chamber for a 3 minute exposure. No irritation or frostbite was 

observed immediately or 60 minutes following exposure. Next, HF0-1234ze(E) 

was applied to the back of 3 rabbits in a similar manner for a 4 hour 

exposure. No irritation or frostbite was observed 60 minutes, 24, 48, or 

72 hours following exposure. HF0-1234ze is not a dermal irritant in rabbits 

under the conditions of this study.141 

-18-
groups of 5 male and 5 female Sprague-Dawley CD rats that were exposed 

nose only to vapors of HF0-1234ze at levels of 0 (control), 100,000 or 

207,000 ppm for 4 hours. The animals were held for a 14-day observation 

period. No mortality, no clinical signs of toxicity, no treatment-related 

changes to body weight, and no food consumption changes were observed. 

At termination, gross necropsy observations were normal and there were 

no treatment-related or statistically significant differences in absolute or relative organ weights (kidneys, liver and lungs). The 4-hour LC50 for 

HF0-1234ze(E) is greater than 207,000 ppm. Based on these results, HF0-

1234ze(E) is considered practically nontoxic by the inhalation route of 

exposure.151 

b. In an acute cardiac sensitization study, a group of 6 beagle dogs were 

exposed to vapors of HF0-1234ze(E) at concentrations of 2%, 6% or 12% 

(20,000, 60,000 or 120,000 ppm). Exposures were conducted on different 

days; with at least a 2-day separation. Initially a determination was made 

for the maximum level of epinephrine that would not cause a cardiac 

arrhythmia. The dogs were then exposed to the test substance for a total of 

10 minutes. After the first five minutes of exposure, each dog received an 

injection of epinephrine at the pre-determined maximum sub-arrhythmia 

dose. During the next five minutes of exposure, the dogs were monitored 

for the development of a cardiac arrhythmia. No arrhythmias or other signs 

of toxicity were induced in any of the dogs. Thus, it was concluded that 

exposure of dogs to a level of 12% (120,000 ppm) of HF0-1234ze(E) did not 

cause cardiac sensitization when challenged with epinephrine.161 

7. Anesthetic and Central Nervous System effects: 

In the GLP acute 4-hour inhalation toxicity study described above, none 

of the Sprague-Dawley CD rats that were exposed to vapors of HF0-

1234ze(E) at levels up to 207,000 ppm for 4 hours showed any evidence of 

anesthetic or CNS effects.151 

- 19-
1) Subacute Toxicity 

a) A GLP 2-week inhalation toxicity study was conducted with four groups of 5 male 

and 5 female Sprague Dawley rats that were exposed nose only to vapors of HF0-

1234ze(E) at levels of 0 (control), 5,000, 20,000 or 50,000 ppm for 6-hours/day, 5 

days/week during a 2 week period, with a total of 10 exposure days. There were 

no treatment-related changes in clinical observations, body weight gain, food 

consumption or food conversion efficiency. Hematologic analysis, clinical 

chemistry analysis, organ weight measurements, and macroscopic and 

microscopic examination of the heart, liver and nasal passages revealed treatment related 

effects in animals exposed to 20,000 and 50,000 ppm. The main effects 

were concentration-related and occurred in the heart (muscle fiber vacuolation and 

mononuclear cell infiltrates) and liver (hepatocellular vacuolation and mononuclear 

cell infiltrates) of animals exposed to 20,000 and 50,000 ppm and in the nasal 

passages (decreased goblet cell expression) of animals exposed to 50,000 ppm. 

Thus 5,000 ppm was considered to be the NOEL for HF0-1234ze(E) in this studyY1 

b) A GLP 4-week inhalation toxicity study was conducted with five groups of male and 

female Sprague Dawley rats exposed nose only to vapors of HF0-1234ze(E) at levels 

of 0 (control), 1,000, 5,000, 10,000 and 15,000 ppm for 6-hours/day, 5 days/week 

during a 4 week period, with a total of 20-21 exposure days. As an additional 

component of this study, at necropsy, liver cells from male rats in the control, 5,000 

and 15,000 ppm groups were evaluated in an Unscheduled DNA Synthesis Test 

and bone marrow from male rats in the control, 5,000, 10,000 or 15,000 ppm 

groups was assessed in a Micronucleus Test. Results of these two genotoxicity 

assays are presented below under the heading Genotoxicity. No treatment-related 

changes were observed when clinical observations, body weight gain, food 

consumption or food conversion efficiency were evaluated. Although clinical 

chemistry analysis showed some variations, they did not appear in a concentration related 

pattern and thus, they were not considered treatment-related. At necropsy, 

no treatment-related macroscopic changes or changes in organ weights were 

-20-
2) Subchronic Toxicity 

A GLP 13-week inhalation toxicity study was conducted with four groups of 10 male 

and 10 female Sprague Dawley rats that were exposed to vapors of HF0-1234ze(E) 

at levels of 0 (control), 1,500, 5,000, or 15,000 ppm for 6 hours/day, 5 days/week 

during a 13-week period, with a total number of 63-64 exposure days. No 

treatment-related changes were observed when clinical observations, body weight 

gain, food consumption or food conversion efficiency were evaluated. Analysis of 

hematology parameters and clinical chemistry showed some slight variations at 

15,000 ppm which may be treatment-related. At necropsy, no treatment-related 

gross changes were observed during macroscopic examination and no treatment related 

organ weight changes were observed. However, microscopic examination 

revealed multifocal mononuclear cell infiltrates in the heart of both sexes at 15,000 

ppm. Fibrosis of the cardiac tissue was not observed. Based on these results, 

15,000 ppm was considered a Low-Observed-Adverse-Effect Level (LOAEL) and 

5,000 ppm was considered the No-Observed-Effect Level (NOEL) for a 13-week 

exposure to HF0-1234ze(E).131 

3) Chronic Toxicity/Carcinogenicity 

No chronic studies were identified. 

4) Reproductive/Developmental Toxicity 

a) In a GLP developmental toxicity study, groups of 24 mated female rats were 

exposed nose only, to levels of 0 (control), 1,500, 5,000 or 15,000 ppm of HF0-

1234ze(E) for 6 hours/day on days 6-19 of gestation. There was no mortality. No 

effect was seen on body weight or food consumption and clinical observations for 

all groups were unremarkable. There were no significant differences in fecundity 

index, number of corpora lutea, the number of implantation sites, the number of live 

fetuses, the post implantation loss, or sex ratio of the pups. In the pups, there were 

no statistically significant differences in visceral or skeletal findings. It was 

- 21 -
concentrations for a definitive prenatal developmental toxicity study. Four groups 

of time-mated female New Zealand rabbits (6/group) were exposed by whole-body 

inhalation to 0 (control), 1,500, 5,000 or 15,000 ppm HF0-1234ze(E) for 6 hours/day 

during gestation days 6 to 28. All animals survived to the scheduled necropsy on 

gestation day 29. No signs of maternal toxicity were observed. Intrauterine growth 

and survival were unaffected by maternal exposure to all exposure levels. No 

external fetal malformations or developmental variations were found. It was 

concluded that inhalation exposures up to 15,000 ppm HF0-1234ze(E) to pregnant 

rabbits did not cause maternal or developmental toxicity in this pilot study.181 

c) A GLP inhalation prenatal developmental toxicity study of HF0-1234ze(E) in rabbits 

was conducted. Four groups of time-mated female New Zealand rabbits 

(22/group) were exposed by whole-body inhalation to 0 (control), 1,500, 10,000 or 

15,000 ppm HF0-1234ze(E) for 6 hours/day during gestation days 6 to 28. All 

animals survived to the scheduled necropsy on gestation day 29. No signs of 

maternal toxicity were observed. Intrauterine growth and survival were unaffected by maternal exposure to all exposure levels. It was concluded that inhalation 

exposures up to 15,000 ppm HF0-1234ze(E) to pregnant rabbits did not cause 

maternal or developmental toxicity. 191 

d) A GLP 2-generation reproductive study was conducted by inhalation with HF0-1234ze(E) in 

Sprague-Dawley Cri:CD(SD) rats. Groups of 24 male and 24 female rats were exposed to levels of 0 

(control), 2,000, 5,000 and 20,000 ppm of HF0-1234ze, 7 days/week for 10 weeks prior to mating, 

during mating, gestation until Day 20 (females) and from 4 days postpartum until the end of 

lactation. Mortality occurred in females in the high exposure level group (20,000 ppm) in both the Fo 

and F1 generations. Seven females in the Fo generation were either found dead or sacrificed in 

extremus late in the lactation phase. Two females in the F1 generation were found dead on lactation 

days 14 and 15. One femalein the Fo generation appeared to have a brain lesion, there was no other 

apparent cause of death in the other rats. There were no other compound related findings in either 

the Fo or F1 generations, including clinical observations, body weights, food consumption, mating 

or fertility, gestation, lactation, parturition, sexual maturation, organ weights or microscopic 

-22-
1. In Vitro 

a. An Ames assay screen was conducted with the bacteria Salmonella 

typhimurium (strains TA1535, TA1537, TA98, and TA100) and Escherichia 

coli (strain WP2 uvrA) both with and without metabolic activation from a rat 

liver preparation. Each strain was exposed to a single exposure level of 5% 

(50,000 ppm) HFO 1234ze(E). Under the conditions of this assay, HF0-1234ze(E) 

did not show any evidence of mutagenic activity.1111 

b. A GLP Ames assay was conducted with HF0-1234ze(E) which involved 

exposure of bacterial strains TA 1535, TA1537, TA 98, TA 100 and WP2 uvrA 

both with and without S-9 metabolic activation. Exposure levels of up to 76% 

(plus 19% 02 and 5% C02) were used. HF0-1234ze(E) did not induce a 

response in any strain tested either without or in the presence of metabolic 

activation.1121 

c. A GLP Chromosome Aberration Test was conducted with cultured human 

lymphocytes that were exposed to vapors levels of HF0-1234ze(E) up to 76%, 

both with and without S-9 metabolic activation. Under the conditions of this 

test, HF0-1234ze(E) was not clastogenic.1131 

2.1n Vivo 

a. A Mouse Micronucleus Assay was conducted following a single 4-hour 

exposure to 29,208 ppm HF0-1234ze(E). At 48 and 72 hours after exposure, 

peripheral blood smear samples were obtained from 5 male and 5 female 

exposed mice, as well as from negative and positive control animals. It was 

concluded that a 4-hour exposure to 29,208 ppm HF0-1234ze(E) did not cause 

chromosome damage in the peripheral blood of exposed mice.1141 

b. A second Micronucleus Assay was conducted with 10 male and 10 female 

CD-1 mice that were exposed by nose-only inhalation to 103,300 ppm HF0-

1234ze(E) for 4 hours. At 24- and 48-hours after exposure, bone marrow cells 

-23-
c. A rat Micronucleus Test was included in the 4-week inhalation toxicity study 

(described above). In that study groups of male and female Sprague-Dawley 

rats were exposed nose only to vapors of HF0-1234ze(E) at levels of 0 (control), 

1,000, 5,000, 10,000 or 15,000 ppm 6-hours/day, 5 days/week during a 4-

week period. At necropsy, bone marrow from male rats in the control, 5,000, 

10,000 or 15,000 ppm groups was used in the Micronucleus Test. At the 

highest concentration tested (15,000 ppm), no damage to chromosomes or 

increased incidence of micronuclei was observed in the bone marrow cells of male rats.12> 

d. An Unscheduled DNA Synthesis Test was also included in the 4-week 

inhalation toxicity study (described above). At necropsy, liver cells from male 

rats in the control, 5,000 and 15,000 ppm groups were used in the 

Unscheduled DNA Synthesis Test. At the highest concentration tested 

(15,000 ppm), no unscheduled DNA synthesis was observed in the liver cells 

of male rats.12> 6) Metabolism/Pharmacokinetics 

HF0-1234ze(E) did not undergo any measurable metabolism when rats were exposed 

to levels up to 5% HF0-1234ze(E) for a single 4-hour period.115> 

7) Genomics 

Statistical analysis of rodent gene expression changes were conducted as part of 

the comprehensive toxicological assessment of HF0-1234ze(E). This was not a 

guideline study, was not GLP compliant, and is not accepted as a validated method 

by the regulatory authorities; however, it was conducted to provide additional 

information. Gene expression changes in liver, kidney and lung tissue were 

assessed following exposure of female B6C3F1 mice and male F344 rats to levels 

of 5,000 and 15,000 ppm HF0-1234ze(E) 6-hrs/day, 5 days/wk for 13 weeks. The 

assessment was based on the results from a comparison of the responses seen 

-24-
selected tissues was conducted. 

Statistical classification analysis predicted HF0-1234ze(E) to be noncarcinogenic in 

both female mouse liver and male rat kidney. A positive response was seen with 

the female mouse lung. There was no dose response relationship with respect to 

changes in gene expression. Furthermore, as only a limited number of genes were 

altered, it was concluded that for the female mouse lung, the number of genes 

altered was too small to perform a meaningful gene ontology enrichment analysis. 

No treatment related histopathological lesions were observed in the liver or kidney 

and only 1/10 mice in both exposure groups showed mild irritation in the lung. 1161 

RECOMMENDED WEEL GUIDE 

A WEEL OEL has been approved by the WEEL Committee for HF0-1234ze(E). It recommends 800 

ppm as an 8-hour TWA.1171 

MATERIAL SAFETY DATA SHEET 

A Honeywell Material Safety Data Sheet for SolsticeTM ZE Refrigerant is attached.1181 

RECOMMENDED ATEL for HFC-1234ze(E) 

4-hr LC50 > 207,000 ppm (v/v) 

Cardiac sensitization NOEL: >120,000 ppm (v/v) 

Anesthetic/CNS effect NOEL:> 207,000 ppm (v/v) 

80% > 166,000 ppm (v/v) 

Other escape impairing effects: None have been identified. 

Oxygen Deprivation Limit: 140,000 ppm, per Section 7.1.2 of Standard 34-2010. 

ATEL: 59,000 ppm (v/v) 

REFERENCES 

(1) Subacute (2-week) Inhalation Toxicity Study with HF0-1234ze in rats. TNO Study 

6456, 25 August 2006, TNO Quality of Life, Zeist, The Netherlands - conducted for 

Honeywell International, ref. MA-RR-06-2838. 

(2) Sub-acute (4-week) Inhalation Toxicity Study, including Unscheduled DNA 

-25-
Study 7383, 28 March 2008, TNO Quality of Life, Zeist, The Netherlands -

conducted for Honeywell International, ref. MA-RR-08-4095. 

(4) Primary Dermal Irritation/Corrosion in Rabbits: HF0-1234ze. MB Research 

Laboratories Study MB-09-18677.03, Spinnertown, PA conducted for Honeywell 

International ref. MA-RR-10-4295. 

(5) An Acute (4-hour) Inhalation Toxicity Screening Study with a Micronucleus Assay 

in the Mouse and Rat via Nose-only Exposure. Study No. 03-5472, 30 March 

2004, Huntingdon Life Science, East Millstone, NJ conducted for Honeywell 

International, ref.MA-RR-04-2768. 

(6) Acute Cardiac Sensitization Study of HF0-1234ze and HF0-1234yf in Dogs. WIL 

Study No. WIL-447008, 23 August, 2006WIL Research Laboratory, Ashland, Ohio 

conducted for Honeywell International, ref. MA-RR-06-2806. 

(7) Prenatal Developmental Inhalation Toxicity Study with HF0-1234ze in Rats. TNO 

Study V 7384. TNO Quality of Life, Zeist, The Netherlands conducted for 

Honeywell International, ref. MA-RR-08-4004. 

(8) An Inhalation Range-Finding Prenatal Developmental Toxicity Study of HF0-

1234ze (1,1,1,3-Tetrafluoropropene) in Rabbits. WIL Study No. WIL-447020, WIL 

Research Laboratories, LLC, Ashland, Ohio 44805 conducted for Honeywell 

International, ref. MA-RR-08-4092. 

(9) HF0-1234ze: Embryo-fetal Toxicity Study in Rabbits via Whole-body Inhalation 

Exposure. HLS Study No. 09-4350, Huntingdon Life Science, East Millstone, NJ, 

May 2010, conducted for Honeywell International ref. MA-RR-10-4302. 

(10) HF0-1234ze: Two-generation reproductive performance study by inhalation administration to 

CD rats. HLS Study No. NBJ0085, Huntingdon Life Sciences, Ltd., Huntingdon, 

Cambridgeshire, PE18 6ES, England conducted for Honeywell International, 

ref.MA-RR-13-4361 (19 March 2013). 

-26-
(12) Mutagenicity Test of (E)-1,3,3,3-Tetrafluoroprop-1-ene Using Microorganisms. 

Japan Bioassay Research Center Study 6301, conducted for Honeywell 

International, Jan. 26, 2009. ref. MA-RR-09-4266 

(13) Chromosome Aberration Test with HF0-1234ze in Cultured Human Lymphocytes. 

TNO Study 6202/08, 8 November 2005, TNO Quality of Life, Zeist, The 

Netherlands- conducted for Honeywell International, ref. MA-RR-05-2810. 

(14) HF0-1234ze, cis (512-96A): Mouse Peripheral Blood Micronucleus Test, 

Huntingdon, report date July 3, 1997, conducted for Honeywell International, ref. 

MA-RR-97 -2380. 

(15) P. Schuster, R. Betermann, G.M. Rusch and W. Dekant. Biotransformation of 

trans-1,3,3,3-tetrafluyoropropene (HF0-1234ze). Toxicology and Applied 

Pharmacology, in press (2009). 

(16) Toxicological Assessment of the Carcinogenic Potential of HF0-1234ze. CIIT 

Report 06014, Hamner Institutes for Health Sciences, Research Triangle Park, NC, 

conducted for Honeywell International, ref. MA-RR-07-3453 (January 5, 2007). 

(17) 1 ,3,3,3-tetrafluoropropene. Workplace Environmental Exposure Level. Occupational Alliance 

for Risk Science (OARS), Workplace Environmental Exposure Levels (WEEL), (2013). 

(18) Honeywell (August 10, 2012). Material Safety Data Sheet SolsticeTM ZE Refrigerant, Honeywell 

International, Inc., 101 Columbia Road, Morristown, NJ 07960. 

-27-
c. NIOSH IDLH: Not established 

d. 4-hr LC50 rat = No data available e. LDso: Not applicable to gas 

f. Cardiac sensitization: No data available 

Chronic Toxicity 

a. ACGIH TLV-TWA or TVL-C: None 

b. AIHA WEEL: None 

c. OSHA PEL or Recommended Exposure Level 880 ppm v/v 

(Blend TLV-TWA is based on the AIHA WEEL values for HFC-134a and HF0-1234ze(E). Toxicity was 

considered additive and the calculation method is that described for Threshold Limit Values for 

Mixtures (ACGIH, 2008). 

Recommended Blend ATEL for ASHRAE Standard 34: 72,000 ppm v/v (See table below for input values.) 

Cardiac 

Lethality Sensitization Anesthetic Effects 

Component 4-hr LCso NOEL LOEL ECso NOEL LOEL 

ppm v/v ppm v/v ppm v/v ppm v/v ppm v/v ppm v/v 

HFC-134a >359,000 50,000 ---------- 270,000 ----------- ----------HF0-1234ze(E) >207,000 >120,000 --------- ----------- ---------- 207,000 

-28-
Section 4: Flammability Information 

-29-
as required in ASHRAE Standard 34-2010 and described in Appendix 81 to ASHRAE Standard 34-

2010. Test conditions were RT and 60°C for the WCF and WCFF. Air used had a humidity of 0.0088 gm water vapor/gm dry air which equates to 50% relative humidity at 23.0°C and 1 atm. 

R-134a/1234ze(E) was found to be non-flammable at the WCF and WCFF when tested at ambient 

and 60°C in air, 1 atm pressure, 50%RH (at 23°C). A heat of combustion of 8.69 MJ/kg was 

calculated using the calculation method of ASHRAE 34-2010. 

This data anticipates a flammability classification of 1. 

Method 

The testing was performed per ASHRAE's current Standard 34-2010 test protocol (condition and 

apparatus) using the current method ASTM E681-04 annex A1. The testing was performed with the 

0.4 second duration spark from the secondary of a 15kV 30 rnA illumination transformer. The 

electrodes were L-shaped 1 mm tungsten wire with a gap of % inch. The igniter was placed above the 

bottom of the flask at a height equivalent to 1/3 diameter of the flask. The vessel was a 12-liter flask. 

The test conditions were ambient and aooc temperatures using 0.0088 g water/g dry air (50% RH air 

at 23°C, dew point of 10.9-12.6°C}. Flame propagation is defined as flames that having spread 

upward and outward to the walls of the flask, are continuous along an arc that is greater than that 

subtended by an angle equal to 90°, as measured from the point of ignition to the walls of the flask. 

The flame shall be continuous along the flask wall. See Figure 4.1. 

Mixtures were made by evacuating the flask and using partial pressures in filling to the desired 

concentration. The air was introduced rapidly to assist in mixing and allowed to come to temperature 

equilibrium. Pressure was measured using a pressure transducer reading to an accurracy of +/-0.3 

mmHg. A two minute pause was allowed after mixing to allow the mixture to stagnate before ignition 

was attempted. 

Figure 4.1 E681 flammability flask and burn/no burn criteria 

-30-
tested was such that if it were possible, flame propagation would have occurred. 

Table 4.1 Composition of WCF and WCFF tested for flammability 

Goal, weight % As determined by 

mass, weight% 

Norminal 

R-134a 42 

R-1234ze(E) 59 

WCF 

R-134a 40 39.9 

R-1234ze(E) 60 60.1 

WCFF 

R-134a 17.3 16.6 

R-1234ze(E) 82.7 83.4 

The WCFF, by the largest amount of flammable, R-1234ze(E), is the final liquid at boiling point +10oc 

which is-13.2°C. 

Experimental Results 

Our internal testing on R-134a/1234ze(E) flammability has shown, by strict adherence to ASHRAE 34, 

to be flammability class 1. 

R-134a/1234ze(E) Flammability testing at (50%RH), 12 liter flask, spark ignition, ambient pressure of 

7 40-750mmHg 

WCFF at sooc using 50% RH at 23°C airR-134a/1234ze(E) (17.3/82.7 mass%) 

Table 4.2 WCFF flammability testing 

-31 -
94 6 60 0 746 Nonflammable 93 7 60 0 746 Nonflammable 92 8 60 0 746 Nonflammable 

91 9 60 0 746 Nonflammable 

90 10 60 0 746 Nonflammable 

89 11 60 0 746 Nonflammable 88 12 60 0 746 Nonflammable 87 13 60 0 746 Nonflammable 86 14 60 0 746 Nonflammable 85 15 60 0 743 Nonflammable 

R-134a/1234ze(E) Flammability testing at (50%RH) 12 liter flask, spark ignition, ambient pressure of 

756 mmHg 

WCF at 60°C using 50% RH at 23°C air 

R-134a/1234ze(E) (39.9/60.1 mass%) 

Table 4.3 WCF flammability testing 

Table 4-3 R134a/1234ze(E) WCF 60°C flammability testing 

Refrigerant 

Air WCFF Barometer Result 

Mol% MOLE% T"C Angleo mmHg 

96 4 60 0 756 Nonflammable 95 5 60 0 756 Nonflammable 94 6 60 0 756 Nonflammable 93 7 60 0 756 Nonflammable 92 8 60 0 756 Nonflammable 

91 9 60 0 756 Nonflammable 

90 10 60 0 756 Nonflammable 

89 11 60 0 756 Nonflammable 88 12 60 0 746 Nonflammable 87 13 60 0 746 Nonflammable 86 14 60 0 756 Nonflammable 85 15 60 0 756 Nonflammable 

Validation of Test Accuracy 

Confirmation of method and test results employed in this Application: 

In 1996-1997, an industry round robin testing program was initiated to assess the inter-lab variability 

of flammability measurements using the E681 method referenced in this Standard. This E681 method 

and apparatus were tested using a 40%/60% R32/R134a blend flammability characterization to 

-32-
deviations. Therefore, there is supporting evidence that the results and method used in this 

Application will meet the quality requirements of Standard 34. 

Fractionation 

Flammability Information (ASHRAE Std 34-2010 Section 9.7) Fractionation Analysis (ASH RAE Standard 34-2010 Appendix 82) 

Fractionation analysis was carried out according to instructions in Appendix 82 to ASHRAE Standard 

34-2010. The initial analysis included storage leaks at 90% fill (of maximum DOT fill volume) at -40°C 

or the normal boiling point plus 10°C, 23°C and 54.4°C temperatures, equipment leaks at 15% fill (of 

maximum DOT fill volume) at -40°C or the normal boiling point plus 1 0°C, 23°C and sooc 

temperatures, and charge/recharge through 5 leakage events of 20% of each refrigerant charge. The 

model calculated data and experimental verification data are presented in the following tables and 

graphs. 

Fractionation of the R-134a/1234ze(E) (40/60 wt.%) WCF to give the WCFF R-134a/1234ze(E) 

(82.7/17.3 wt.%), final liquid at the lowest temperature: boiling point plus 10°C (-13.2°C) see Figure 

4.2. 

Figure 4.2 Temperature for WCFF by maximum flammable. 

84.0% 83.0% 82.0% 81.0% 80.0% 

79.0% 78.0% 77.0% 76.0% 75.0% 74.0% 73.0% 

-20 

............ 

-10 

WCFF R1234ze(E) liq 

............... 

............... 

0 10 

............... 

"" 

20 

t ("C) 

"" 

30 

"" 

. 

40 50 60 

RefProp 9.1 Interaction parameter for R-134a/1234ze(E) 

Vapor Liquid Data (VLE) was obtained from pressure temperature bulk composition (PTz) measurements from 0 to 

50"C and 50 to 100% by wt R-1234ze(E) with R-134a. From this data the interaction parameters were determined. A 

zeta of -6.2782 was determined and used for the simulations. 

-33-
39.4 0 39.779942 110.53623 39.4 9.20 39.912822 120.41387 

39.4 0.3 -0.183371 31.304179 39.4 12.00 -0.058006 35.267533 

39.4 0.3 9.673267 44.509269 39.4 12.00 9.681177 49.602247 

39.4 0.3 19.666579 61.84516 39.4 12.00 19.720491 68.441848 

39.4 0.3 29.855891 83.977021 39.4 12.00 29.884035 92.626522 39.4 0.3 39.900707 110.95418 39.4 12.00 39.953619 122.24241 39.4 0.8 -0.055228 31.57798 39.4 13.00 -0.000594 35.337877 39.4 0.8 9.807204 44.826605 39.4 13.00 9.781677 49.89757 

39.4 0.8 19.813566 62.111968 39.4 13.00 19.793617 69.050777 

39.4 0.8 29.953581 84.331382 39.4 13.00 29.931089 93.436881 

39.4 0.8 39.975435 111.04494 39.4 13.00 40.020288 123.32406 

39.4 1.50 -0.147086 31.856336 39.4 13.50 -0.137132 35.469538 39.4 1.50 9.715534 45.177824 39.4 13.50 9.744521 50.211682 

39.4 1.50 19.726754 62.549991 39.4 13.50 19.691942 69.135m 

39.4 1.50 29.804076 85.014623 39.4 13.50 29.886006 93.484855 

39.4 1.50 39.873999 112.21038 39.4 13.50 39.902178 123.38898 39.4 2.90 -0.139527 32.6103 39.4 18.60 -0.186101 36.305549 

39.4 2.90 9.m642 46.146581 39.4 18.60 9.622846 51.216887 

39.4 2.90 19.7175 63.731068 39.4 18.60 19.678988 70.692502 39.4 2.90 29.867294 86.402464 39.4 18.60 29.823014 95.715999 39.4 2.90 39.899089 113.48915 39.4 18.60 39.941814 126.45466 

39.4 3.50 -0.168974 32.782409 39.4 24.00 -0.142926 37.169733 

39.4 3.50 9.598093 46.320468 39.4 24.00 9.599927 52.1694 

39.4 3.50 19.637972 64.125745 39.4 24.00 19.661538 72.067082 

39.4 3.50 29.786734 87.018567 39.4 24.00 29.840108 97.502434 

39.4 3.50 39.89027 115.02216 39.4 24.00 39.871917 128.76566 

39.4 4.70 -0.231923 33.136565 39.4 29.00 -0.304235 37.265101 

39.4 4.70 9.716375 46.958981 39.4 29.00 9.770066 52.997329 39.4 4.70 19.725816 64.907543 39.4 29.00 19.813624 73.19836 

39.4 4.70 29.895023 87.831036 39.4 29.00 29.889062 98.747342 

39.4 4.70 39.885432 115.6945 39.4 29.00 39.902654 130.20329 

39.4 5.60 -0.110744 33.357096 39.4 32.10 0.078285 37.871582 39.4 5.60 9.676343 47.168594 39.4 32.10 9.726329 53.165443 39.4 5.60 19.702566 65.273685 39.4 32.10 19.641596 73.553109 

39.4 5.60 29.932944 88.415793 39.4 32.10 29.829219 99.470416 

39.4 5.60 39.96353 116.74799 39.4 32.10 39.91474 131.26652 

39.4 5.90 -0.13282 33.521774 39.4 35.60 -0.278378 37.906192 39.4 5.90 9.719808 47.311931 39.4 35.60 9.644785 53.537022 

39.4 5.90 19.739405 65.408996 39.4 35.60 19.691286 74.103699 

39.4 5.90 29.905738 88.699371 39.4 35.60 29.856418 100.18354 

39.4 5.90 39.9917 117.23338 39.4 35.60 39.850385 131.96774 

39.4 6.40 -0.17575 33.643662 39.4 40.50 -0.23725 38.225126 39.4 6.40 9.674895 47.575364 39.4 40.50 9.732334 54.286065 

39.4 6.40 19.692253 65.779693 39.4 40.50 19.689228 74.861835 

39.4 6.40 29.831678 89.089433 39.4 40.50 29.858518 101.16579 

39.4 6.40 39.836632 117.60515 39.4 40.50 39.861647 133.59816 39.4 7.40 -0.106019 33.934891 39.4 7.40 9.680547 47.822705 

39.4 7.40 19.711599 66.156477 

39.4 7.40 29.799061 89.661898 39.4 7.40 39.7876 117.99261 

-34-
10 0.153352 60.84% 39.16% 53.14% 46.86% 

20 0.152893 61.75% 38.25% 54.04% 45.96% 

30 0.152364 62.80% 37.20% 55.07% 44.93% 

40 0.151743 64.01% 35.99% 56.26% 43.74% 

50 0.150995 65.44% 34.56% 57.70% 42.30% 

60 0.150061 67.20% 32.80% 59.48% 40.52% 

70 0.148831 69.46% 30.54% 61.81% 38.19% 

80 0.147057 72.60% 27.40% 65.13% 34.87% 

90 0.143961 77.81% 22.19% 70.87% 29.13% 

95 0.140873 82.69% 17.31% 76.54% 23.46% 

-35-
60.0% 

:;:: 

8 500% E . 

,, 

g 

0 . 

v 

20.0% 

10.0% 

0.0% 

' 

0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0"/0 30.0% 90.0% 100.:J% 

Leak '1Vt0 o 

90.0% 

80.0% 

70.0% 

60.0% 

. o 

:: 50.0% 

8 

-E ,, 40.0% .._, _____ 0 

e. 

§ 

u 30.0% 

20.0% 

10.0% 

U.U% .J----,-----,---------,-----,.--

0.0')( 10.0% 20.0% 30.0% 40.0% 50.0% 60.0'!f 70.0% 80.0% 90.0% 100.0% 

Leakwt"'o 

- 36-
10 0.549547 61.69% 38.31% 55.32% 

20 0.548235 62.46% 37.54% 56.08% 

30 0.546733 63.34% 36.66% 56.96% 

40 0.544986 64.35% 35.65% 57.97% 

50 0.542902 65.54% 34.46% 59.18% 

60 0.540332 66.98% 33.02% 60.65% 

70 0.537008 68.82% 31.18% 62.55% 

80 0.532352 71.34% 28.66% 65.19% 

-37-

44.68% 43.92% 43.04% 42.03% 40.82% 

39.35% 

37.45% 

34.81% 
60.0% 

.-

c 50.0% -s 

0 '" 

& 40.0% 

.l 0 u 30.0% 

I 

20.0% 

10.0% 

0.0% 

0.0% 20.0% 40.0% 60.0% 80.0% 100.0% 

Leakwt% 

80.0% 

70.0% +-

60.0% 

0 

- vaj)Oir phase Mass Ft ac. R134.a 

50.0% ;;.. 

... 

.-

0 

'_z:j 

- 40.0% 

0 '" 

::::.. 

>:: 

0 30.0% u 

20.0% 

10.0% 

0.0% 

0.0% 20.0% 40.0% 60.0% 80.0% 100.0% 

Leakwt% 

-38-
54.40

C Liquid phase phase 

Leak% Pressure Mass% Mass% 

MPa R-1234ze(E) R-134a R-1234ze(E) R-134a 

0 1.296257 60.04% 39.96% 55.00% 45.00% 

2 1.295845 60.15% 39.85% 55.11% 44.89% 

10 1.294103 60.61% 39.39% 55.56% 44.44% 

20 1.291678 61.25% 38.75% 56.20% 43.80% 

30 1.288909 61.97% 38.03% 56.92% 43.08% 

40 1.285688 62.81% 37.19% 57.76% 42.24% 

50 1.281846 63.80% 36.20% 58.76% 41.24% 

60 1.277102 65.02% 34.98% 59.99% 40.01% 

70 1.270929 66.57% 33.43% 61.57% 38.43% 

80 1.262153 68.75% 31.25% 63.81% 36.19% 90 1.247129 72.37% 27.63% 67.60% 32.40% 

-39-
,c 50.•}% 2::. 

"' 

.§ 

40.0% 

:; 

a. 

§ 

u 30.0% 

lO.O% -- - - -- """ -

lO.O% I 

0.0% -,--- -----,--,- ' - --,-

O.J% l :J.O'K 20.0% 30.0% 40.0% 50.0% 60.0':1, 70.0% 80.0".4 90.0% 

Leak\\1% 

8[).0Jb 

70.0li. --- -

60.0% 

*-

I c:: 

I 

-- - - -

0 

e. 40.0 Yo 

5 

u 

30.0% -

I 

l:l.U% I 

' O.O'X r----.-- lv1G'e_0, O.O'l'< 10.0% 20.0% 3D.O'Yt 40.0% 16 70.C% 80.0% 90.0'!> :oo.o?> 

-40-
Vapor 

-13.21oC Liquid phase phase 

Leak% Pressure Mass% Mass% 

MPa R-1234ze(E) R-134a R-1234ze(E) R-134a 

0 0.153594 60.35% 39.65% 52.67% 47.33% 

2 0.153516 60.51% 39.49% 52.82% 47.18% 

10 0.153187 61.17% 38.83% 53.47% 46.53% 

20 0.152725 62.09% 37.91% 54.37% 45.63% 

30 0.152193 63.13% 36.87% 55.40% 44.60% 

40 0.15157 64.34% 35.66% 56.60% 43.40% 

50 0.150821 65.77% 34.23% 58.03% 41.97% 

60 0.149887 67.52% 32.48% 59.81% 40.19% 

70 0.148662 69.76% 30.24% 62.12% 37.88% 

80 0.146911 72.86% 27.14% 65.41% 34.59% 

90 0.143933 77.86% 22.14% 70.92% 29.08% 

95 0.141159 82.25% 17.75% 76.02% 23.98% 

-41 -
.... 

§ 

·-= •r. 0 

:::; =-

8 

.o 

0 

"§ 

'

0 " §< 

0 

u 

r 60.0% 

SO.O'!o 

40.0% 

30.0% 

20.0% 

10.0% 

0.0% ·1-----r---..----r------,.-----

G.Oo/.. 10.0",{ 20.0'¥. 30.0\i 4J.Ol0 50.0% 60.0% 70.J% 80.0"/o 90.0% 103.0% 

Leak 

80.0% 

70.0% 

60.0% 

50.0% 

40.0% 1--------

30.0% 

20.0% 

10.0% ·1---------------------------

0.0% 

0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0% 

Leakwt% 

-42-
q

p

p

(

) 

23.oooc Liquid phase Vapor phase 

Leak% Pressure Mass% Mass% 

MPa R-1234ze(E) R-134a R-1234ze(E) 

0 0.550712 61.00% 39.00% 54.63% 

2 0.550489 61.13% 38.87% 54.76% 

10 0.549547 61.69% 38.31% 55.32% 

20 0.548235 62.46% 37.54% 56.08% 

30 0.546733 63.34% 36.66% 56.96% 

40 0.544986 64.35% 35.65% 57.97% 

50 0.542902 65.54% 34.46% 59.18% 

60 0.540332 66.98% 33.02% 60.65% 

70 0.537008 68.82% 31.18% 62.55% 

80 0.532352 71.34% 28.66% 65.19% 

-43-

R-134a 

45.37% 45.24% 44.68% 43.92% 

43.04% 42.03% 40.82% 

39.35% 37.45% 34.81% 
[ 

j ::: 1----------·---------- +

m 

0 

§ 30.0<;(; u 

l 

JQ.(}% --

(•.0% L- --, 

0.:>% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 80.0Yo 

Leak wt• .• 

, ... [ 

60.0% -

50.0% 

--Vapor phase Mass Frac. R 134a 

0 

40.0% 

.... 

0 

a. 

:::: 

30.0% - --- -

0 

u 

20.0% 

10.0% 

0.0% I T 

0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 

Leak wt'lo 

-44-

90.0% 

90.0% 
2 1.473331 62.30% 37.70% 57.51% 42.49% 

10 1.471405 62.74% 37.26% 57.96% 42.04% 

20 1.468734 63.34% 36.66% 58.57% 41.43% 

30 1.4657 64.03% 35.97% 59.26% 40.74% 

40 1.462194 64.82% 35.18% 60.05% 39.95% 

50 1.458052 65.74% 34.26% 60.99% 39.01% 

-45-
40.0% f 

0 

.0: 

§' 30.0'JG 

s 

u 

20.()10 

10.0% I 

O.()l(, 

0.0% IOOl> 10.0'14 40.0% SO.O"-' GO.Ole, 

70.00.6 

60.0% t 

50.0% I 

,o 

O' 

§ 40.0% I 

.::l 

lil 

0 30.0% +--

u 

20.0% I 

10.0% 

0.0% l 

0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 

-46-
10% 0.549547 61.69% 38.31% 55.32% 44.68% 

20% 0.548235 62.46% 37.54% 56.08% 43.92% 

20% 0.549123 61.94% 38.06% 55.56% 44.44% 

30% 0.547947 62.63% 37.37% 56.25% 43.75% 

40% 0.546622 63.40% 36.60% 57.02% 42.98% 

40% 0.54784 62.69% 37.31% 56.31% 43.69% 

50% 0.546655 63.38% 36.62% 57.00% 43.00% 

60% 0.545321 64.15% 35.85% 57.78% 42.22% 

60% 0.546806 63.29% 36.71% 56.91% 43.09% 

70% 0.545614 63.98% 36.02% 57.61% 42.39% 

80% 0.544274 64.75% 35.25% 58.38% 41.62% 

80% 0.545975 63.78% 36.22% 57.40% 42.60% 

90% 0.544778 64.46% 35.54% 58.09% 41.91% 

100% 0.543432 65.23% 34.77% 58.87% 41.13% 

-47-
...... 50.0% 

:::: - Liquid Phase Mass Frac. R134a 

..... 0 40.0% ..... 

0 

-

.-4 

rn 

-

0 -

30.0% ..... ...... 

0 

C) 

20.0% 10.0% 

0.0% 

0.0 0.2 0.4 0.6 0.8 1.0 

Leakwt% 

70.0% 

60.0% -1 - VaporPhase Mass Frac. R1234ze 

- -

50.0% -1 

' 

..... I 

. gW.O% -! 

• v aDor Pbase Mass Frac. R 134a 

.... rn 

0 

§30.0% 

1 

.... 

0 

C) 

20.0% 

10.0% 

0.0% 

0.0 0.2 0.4 0.6 0.8 1.0 

Leakwt% 

-48-
temperature by housing in an environmental chamber. 

Once the test vessel had been charged with refrigerant, it was brought to the appropriate temperature. 

Initial liquid and vapor samples were taken for gas chromatographic (GC) analysis. The refrigerant 

vessel inside the constant temperature bath was connected to a mass flowmeter. The refrigerant was 

leaked at a nominal rate of 2% of the total mass charged per hour. 

This continued until the internal pressure of the vessel was at ambient pressure or no liquid phase 

remained, or 95% of the mass had leaked. 

Liquid and vapor samples were analyzed for composition following the procedure below. 

Procedure for Fractionation Composition Analysis of R-134a/1234ze(E): 

• Prepare the refrigerant blend sample to the exact specification in a stainless steel cylinder 

such that the test vessel will be at 90% of DOT fill. 

• The leaking vapor was sampled and a GC was used to determine composition .. 

• The leak was stopped and liquid sampled at about 10% weight loss intervals. 

Analysis: 

The sample was analyzed in the vapor phase to determine t composition more accurately, 

avoiding any VLE from condensate or dew. 

Determination of composition by Gas Chromatography: 

GC equipped with a thermal conductivity detector (TCD) was used. The 

GC column was a packed column, Chromosorb P 80/100 1/8" 10m, helium carrier gas. 

GC Method: Initial temp. 50.C 

Initial time 10 min 

Rate 1 1 0 deg/min 

Final Temp. 150 deg Hold time 0 min 

Injector temp 200 deg 

Detector 300 deg 

Detector type TCD Pressure 51.3psi 

Data Acquisition: Perkin Elmer Totalchrom 

Composition Calculation: 

The normalized weight% of each component in the blend at -13.5°C was computed from a 

comparison of their individual peak areas with those of the respective calibration standards. 

GC standards were made for the 

-49-
oftheWCFF. 

Plotted below is the R-134a/1234ze(E) experimental data and REFPROP 9.1 output. This data 

agrees well with REFPROP 9.1. 

Experiments were carried out at -13.5°C and the results verify REFPROP 9.1 with the experimentally 

determined interaction parameters as a suitable model for this system. 

Table 4.12 Experimental fractionation data 

experimental 

data R-134a R-1234ze(E) R-134a R-1234ze(E) 

wt% loss liq liq vap vap 

0.00% 40.44% 59.56% 47.33% 52.67% 

1.95% 40.43% 59.57% 47.24% 52.76% 

8.95% 39.83% 60.17% 46.69% 53.31% 

17.43% 39.14% 60.86% 46.14% 53.86% 

26.41% 38.32% 61.68% 45.27% 54.73% 

35.64% 37.31% 62.69% 44.28% 55.72% 

44.94% 36.24% 63.76% 43.14% 56.86% 

54.24% 34.90% 65.10% 41.86% 58.14% 

64.14% 32.97% 67.03% 40.10% 59.90% 

73.32% 30.89% 69.11% 37.77% 62.23% 

Table 4.13 Simulated RefProp 9.1 data at the same temperature as the Experimental fractionation data 

-13.50oC Liquid phase Vapor phase 

Leak% Pressure Mass% Mass% 

MPa R-1234ze(E) R-134a R-1234ze(E) R-134a 

0 0.141447 59.52% 40.48% 51.80% 48.20% 

2 0.141376 59.67% 40.33% 51.95% 48.05% 

10 0.141073 60.34% 39.66% 52.59% 47.41% 

20 0.140649 61.27% 38.73% 53.49% 46.51% 

30 0.14016 62.32% 37.68% 54.52% 45.48% 

40 0.139586 63.54% 36.46% 55.72% 44.28% 

50 0.138893 64.99% 35.01% 57.16% 42.84% 

60 0.138028 66.76% 33.24% 58.95% 41.05% 

70 0.136885 69.04% 30.96% 61.30% 38.70% 

80 0.135234 72.23% 27.77% 64.66% 35.34% 90 0.132342 77.52% 22.48% 70.47% 29.53% 

95 0.129444 82.49% 17.51% 76.23% 23.77% 

-50-
90.0% - Lt td Mass Frac. R 1234z:e 

--LiqutdpbaseMassFrac R134a 

80.0% 

70.0% 

i 60.0% 

?: 

.... 

50.0% I 

... 

0 . • .. • 

v 

0 

C ' 

.... 

. _g 

0 

;a. 

§ 

C) 

--......___. 30.0% .,--.. ---------------------- =,.... .. = -------

- 20.0% 

10.0% 

0.0% 

0.0% 10.0% 20 ()",(, 30.0% 40.0% 50.0% 60.0% 70 0% 80.0% 90.0% 100 0% 

80.0% 

70.0% 

60.0% 

50.0% 

40.0% 

30.0% 

20.0% -!---

Leakwt% 

Mass Frac- R1234ze 

Vapor phase Mass Frac R 134a 

---------------------------------------------

10.0% +----------------------------------------------------

0.0% 

0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0% 

Leak '"i'!·o 

-51 -
If there is insufficient hydrogen (H) available for the formation of HF(g), HCI(g), and H20(g), then the 

formation of HF(g) takes preference over the formation of HCI(g), which takes preference over the 

formation of H20. If there is insufficient hydrogen available for all of the fluorine (F) to form HF(g), 

then the remaining fluorine produces COF2 (g) in preference of carbon (C) forming C02. Any 

remaining chloride (CI) produces Cl2 (g) (chlorine). 

0.447325 C2H2F4 + 0.5526745317 C3H2F4 +2.052672 02 => 1.552672 C02+ 2 HF+ 1 COF2 

The heat of reaction for the combustion of R-134a/1234ze(E) is 

0.447325*(-895.376)+0.552674*(-816.05) -1.552672*(-393.51) -2*(-273.3) -1*(-638.9) = 944.96 kJ/mol 

R134a/R1234ze(E) nominal has a molecular weight of 108.67 g/mol 

This gives a heat of combustion of kcal/g = 8.69 MJ/kg. 

-52-
Section 5: RCL Value I Contaminants and Impurities 

-53-
ATEL: 72,000 ppm (v/v) 

ODL (Oxygen Deprivation Limit): 140,000 ppm, per Section 7.1.2 of Standard 34-2010. 

LFL: none 

Burning Velocity: not applicable 

RCL: 72,000 ppm (v/v) 

Contaminants and Impurities (ANSI/ASHRAE Standard 34-2010 Section 9.8) 

Toxicity and Flammability: 

There are no known contaminants or impurities, including isomeric and 

decomposition impurities from manufacturing, transport, and storage known to 

increase the flammability or toxicity within the precision of the RCL. 

-54-
Section 6 - Appendices 

Appendix 1: MSDS, Subject Blend Honeywell SolsticerM N13 (HDR-15) 

Appendix 2: MSDS, R-134a 

Appendix 3: MSDS, R-1234ze(E) 

• 55.