AU2005205601A1 - 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane refrigerant compositions comprising a fluoroether and uses thereof - Google Patents

Description

WO 2005/068580 PCT/US2005/001510 TITLE OF INVENTION 1 -ETHOXY-1,1,2,2,3,3,4,4,4-NONAFLUOROBUTANE REFRIGERANT COMPOSITIONS COMPRISING A FLUOROETHER AND USES THEREOF 5 CROSS REFERENCE(S) TO RELATED APPLICATION(S) This application claims the priority benefit of U.S. Provisional Application 60/536,819, filed January 14, 2004, and U.S. Provisional Application 60/537,453, filed January 15, 2004, and U.S. Provisional 10 Application 60/549,978, filed March 4, 2004, and U.S. Provisional Application 60/575,037, filed May 26, 2004, and U.S. Provisional Application 60/584,785, filed June 29, 2004. BACKGROUND OF THE INVENTION 15 1. Field of the Invention. The present invention relates to compositions suitable for use in refrigeration and air conditioning apparatus comprising at least one hydrofluoroether. Further, the present invention relates to compositions suitable for use in refrigeration and air-conditioning apparatus employing a 20 centrifugal compressor comprising at least one hydrofluoroether. The compositions of the present invention may be azeotropic or near azeotropic in nature and are useful in processes for producing refrigeration or heat or as heat transfer fluids. 25 2. Description of Related Art. The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most 30 refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC 134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol. 35 Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants 1 WO 2005/068580 PCT/US2005/001510 used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the automobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for 5 refrigerants that can be used in all areas of the refrigeration and air conditioning industry. Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO2 or ammonia. Many of these suggested 10 replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought. The object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower 15 global warming potential as compared to current refrigerants. BRIEF SUMMARY OF THE INVENTION The present invention relates to refrigerant and heat transfer fluid compositions selected from the group consisting of:

C

4

F

9

OC

2

H

5 and 1-(difluoromethoxy)-1,2,2-trifluoroethane; 20 C 4

F

9 0C 2

H

5 and 1-difluoromethoxy-2,2-difluoroethane;

C

4

F

9

OC

2

H

5 and 2-methoxy-1,1,2-trifluoroethane;

C

4

F

9

OC

2

H

5 and 1,1-difluoro-2-methoxyethane; and

C

4

F

9 0C 2

H

5 and 1-(1,1,2,2-tetrafluoroethoxy)propane. The present invention further relates to the above listed 25 compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor. The present invention further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a multi-stage, preferably two-stage centrifugal 30 compressor. The present invention further relates to the above listed compositions specifically suitable for use in refrigeration or air conditioning apparatus employing a single pass/single slab heat exchanger. The present invention further relates to azeotropic or near 35 azeotropic refrigerant compositions. These compositions are useful in refrigeration or air conditioning apparatus. The compositions are also 2 WO 2005/068580 PCT/US2005/001510 useful in refrigeration or air conditioning apparatus employing a centrifugal compressor. The present invention further relates to processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink 5 using the present inventive compositions. DETAILED DESCRIPTION OF THE INVENTION Disclosed here are compositions comprising C 4 F9OC 2

H

5 and at least one fluoroether. 10 The hydrofluorocarbons of the present invention comprise compounds containing hydrogen, fluorine and carbon. These hydrofluorocarbons may be represented by the formula CxH 2 x+ 2 -yFy. In the formula, x may equal 3 to 8 and y may equal 1-17. The hydrofluorocarbons may be straight chain, branched chain or cyclic 15 compounds having from about 3 to 8 carbon atoms. Preferred hydrofluorocarbons have 3 to 6 carbon atoms and no more than 5 fluorine atoms. Representative hydrofluorocarbons are listed in Table 1. TABLE 1 20 Compound Chemical Formula Chemical Name GAS Req. I I No. Hydrofluoroethers HFOC-236caE CHF 2 0CF 2

HF

2 2 1-difluoromethoxy-1,1,2,2- 32778-11-3 tetrafluoroethane HFOC-236eaEpy CHF 2 0CHFCF3 2-difluoromethoxy-1,1,1,2- 57041-67-5 tetrafluoroethane HFOC-245caEap CHF 2 0CF 2

CH

2 F 1-(difluoromethoxy)-1, 1,2- 69948-24-9 trifluoroethane HFOC-245cbEpy CF 3

CF

2 0CH 3 1,1,1,2,2-pentafluoro-2-methoxyethane 22410-44-2 HFOC-245eaE CHF 2 0CHFCHF 2 1-(difluoromethoxy)-1,2,2- 60113-74-8 trifluoroethane HFOC-245ebEpy CF 3

CHFOCH

2 F 2-fluoromethoxy-1,1,1,2- 56885-27-9 tetrafluoroethane HFOC-245faEap CHF 2

CH

2 0CF 3 1,1-difluoro-2-trifluoromethoxyethane HFOC-245faE3py CF 3

CH

2 0CHF 2 2-difluoromethoxy-1,1,1-trifluoroethane 1885-48-9 HFOC-254cbEpy CHF 2

CF

2

OCH

3 1-methoxy-l,i,2,2-tetrafluoroethane 425-88-7 HFOC-254ebEpy CF 3

CHFOCH

3 2-methoxy-1,1,1,2-tetrafluoroethane 148380-63-6 HFOC-254faE CHF 2 0CH 2

CHF

2 1-difluoromethoxy-2,2-difluoroethane 32778-16-8 HFOC-263ebEpy CH 3

OCHFCHF

2 2-methoxy-1,1,2-trifluoroethane 56281-91-5 HFOC-263fbEpy CF 3

CH

2 0CH 3 2-methoxy-1,1,1-trifluoroethane HFOC-272fbEpy CH 3

OCH

2

CHF

2 1,1-difluoro-2-methoxyethane 461-57-4 HFOC-338mcfEpy CF 3

CF

2 0CH 2

CF

3 1,1,1,2,2-pentafluoro-2-(2,2,2- 156053-88-2 trifluoroethoxy)ethane HFOC- CF 3

CHFOCHFCF

3 1,1'-oxybis(1,2,2,2-tetrafluoro)ethane 67429-44-1 338meeEpy HFOC- (CF 3

)

2

CHOCHF

2 2-(difluoromethoxy)-1,1,1,3,3,3- 26103-08-2 3 WO 2005/068580 PCT/US2005/001510 338mmzEPy hexafluoropropane HFOC-338peEyB CHF 2 OCHF 3-(difluoromethoxy)-1,1,1,2,2,3- 60598-11-0 hexafluoropropane HFOC- CF 3

CF

2

CF

2 0CHa 1,1,1,2,2,3,3-heptafluoro-3- 375-03-1 347mccEy8 methoxypropane HFOC- CF 3

OCF

2

CH

2

CHF

2 1,1,3,3-tetrafluoro-1 347mcfEcp (trifluoromethoxy)propane HFOC-347mcfEpy CHF 2

CH

2

OCF

2

CF

3 1-(2,2-difluoroethoxy)-1,1,2,2,2- 171182-95-9 pentafluoroethane HFOC-347mcfEy8 CHF20CH 2

CF

2

CF

3 3-(difluoromethoxy)-1,1,1,2,2- 56860-81-2 pentafluoropropane HFOC- CF 3

OCH

2

CF

2

CHF

2 1,1,2,2-tetrafluoro-3- 1683-81-4 347mfcEap (trifluoromethoxy)propane HFOC- CH 2 FOCH(CF3) 2 1,1,1,3,3,3-hexafluoro-2- 28523-86-6 347mmzEpy (fluoromethoxy)propane HFOC-347pcfEpy CF 3

CH

2

OCF

2

CHF

2 1-(2,2,2-trifluoroethoxy)-1,1,2,2- 406-78-0 tetrafluoroethane HFOC- CH 3

OCF

2

CHFOCF

3 1,1,2-trifluoro-1-methoxy-2- 996-56-5 356mecE2apy5 (trifluoromethoxy)ethane HFOC- CH 3

OCF

2 CHFCF3 1,1,1,2,3,3-hexafluoro-3- 382-34-3 356mecEy 8 methoxypropane HFOC- (CF3) 2

CHOCH

3 1,1,1,3,3,3-hexafluoro-2- 13171-18-1 356mmzEpy methoxypropane HFOC-356pccEy5 CHF 2

CF

2

CF

2

OCH

3 1,1,2,2,3,3-hexafluoro-3 methoxypropane HFOC-356pcfEpy CHF 2

CF

2

OCH

2

CHF

2 1-(1,1-difluoroethoxy)-1,1,2,2 tetrafluoroethane HFOC-356pcfEy8 CHF 2

OCH

2

CF

2

CHF

2 3-(difluoromethoxy)-1,1,2,2- 35042-99-0 tetrafluoropropane HFOC- CHF 2

OCH(CH

3

)(CF

3 ) 2-(difluoromethoxy)-1,1,1- 327893-56-9 365mpzE3y trifluoropropane HFOC-365mcEy CF 3

CF

2

CH

2

OCH

3 1,1,1,2,2-pentafluoro-3- 378-16-5 methoxypropane HFOC-374mefEI3y CF 3

CHFOCH

2

CH

3 2-ethoxy-1,1,1,2-tetrafluoroethane 50285-06-8 HFOC-374pcEp3y CH 3

CH

2 0CF 2

CHF

2 I-ethoxy-1,1,2,2-tetrafluoroethane 512-51-6 HFOC-383mEcu3 CF 3

OCH

2

CH

2

CH

3 1-(trifluoromethoxy)propane 59426-77-6 HFOC-383mE3y CH 3

CH

2 0CH 2

CF

3 1,1,1-trifluoro-2-ethoxyethane 461-24-5 HFOC-383mEy CF 3

CH

2

CH

2

OCH

3 1,1,1-trifluoro-3-methoxypropane 461-22-3 HFOC-383mzEc4p CH 3 0CH(CH 3

)(CF

3 ) 1,1,1-trifluoro-2-methoxypropane 32793-45-6 HFOC-383peEpy CHF 2

CHFOCH

2

CH

3 1-ethoxy-1,2,2-trifluoroethane 20202-98-6 HFOC-42- CF 3

CF

2 CF20CHFCF 3 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2- 3330-15-2 11 mccEy6 tetrafluoroethoxy)propane HFOC- CF 3 CHFCF20CF 2

CF

3 1,1,1,2,3,3-hexafluoro-3- 142469-07-6 42-11 meEy6 (pentafluoroethoxy)propane HFOC- CH 3

CH

2 0CF(CF 3

)

2 2-ethoxy-1,1,1,2,3,3,3- 22137-14-0 467mmyEoy heptafluoropropane HFOC- CH 3

CH

2

OCF

2

CF

2 CFa 3-ethoxy-1,1,1,2,2,3,3- 22052-86-4 467mccEy8 heptafluoropropane HFOC- CH 3

CH

2 0CH(CF 3

)

2 2-ethoxy-1,1,1,3,3,3-hexafluoropropane 18339-53-8 476mmzEpy HFOC-494pcEPy CH 3

CH

2

CH

2 0CF 2

CHF

2 1-(1,1,2,2-tetrafluoroethoxy)propane 380-48-3 HFOC-494pcEy8 CH 3

CH

2 0CH 2

CF

2

CHF

2 3-ethoxy-1,1,2,2-tetrafluoropropane 24566-96-9 HFOC-494pczEpy' (CH 3 ) 2

CHOCF

2

CHF

2 2-(1,1,2,2-tetrafluoroethoxy)propane 757-11-9 HFOC- c-OCF 2

CHFCHFCF

2 - 2,2,3,4,5,5-hexafluorotetrahydrofuran 24280-80-6 C336ceeEc I_ HFOC- c-OCHFCHFCH(CF 3 )- 2,3-difluoro-4-(trifluoromethyl)oxetane 74985-21-0 C345mzeEp I 4 WO 2005/068580 PCT/US2005/001510 The compounds listed in Table 1 are available commercially or may be prepared by processes known in the art or as described below.

C

4

F

9 0C 2

H

5 is a mixture of isomers and is available commercially from 3 MTM (St. Paul, Minnesota). 5 Compositions of the present invention have no ozone depletion potential and low global warming potential . For example, fluoroethers, alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use. The refrigerant or heat transfer compositions are selected from the 10 group consisting of:

C

4

F

9 0C 2

H

5 and 1-(difluoromethoxy)-1,2,2-trifluoroethane;

C

4

F

9 0C 2

H

5 and 1-difluoromethoxy-2,2-difluoroethane;

C

4

F

9 0C 2

H

5 and 2-methoxy-1,1,2-trifluoroethane;

C

4 FgOC 2

H

5 and 1,1-difluoro-2-methoxyethane; and 15 C 4

F

9 0C 2

H

5 and 1-(1,1,2,2-tetrafluoroethoxy)propane. The refrigerant or heat transfer compositions of the present invention may be azeotropic or near azeotropic compositions. An azeotropic composition is a liquid admixture of two or more substances that has a constant boiling point that may be above or below the boiling 20 points of the individual components. As such an azeotropic composition will not fractionate within the refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from the refrigeration or air conditioning system. In the situation where one 25 component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system. A near azeotropic composition is a substantially constant boiling, liquid admixture of two or more substances that behaves 30 essentially as a single substance. One way to characterize a near azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to 35 characterize a near azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition 5 WO 2005/068580 PCT/US2005/001510 is near azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is 5 less than about 10 percent. The azeotropic refrigerant compositions of the present invention are listed in Table 2. TABLE 2 Azeotrope Azeotrope Component A Component B Concentration BP (oC) Wt% A Wt% B

C

4

F

9 0C 2

H

5 HFOC-245eaE 11.9 88.1 52.7

C

4

F

9 0C 2 Hs HFOC-254faE 26.0 74.0 54.0

C

4

F

9 0C 2

H

5 HFOC-263ebE3py 40.2 59.8 54.0

C

4

F

9

OC

2

H

5 HFOC-272fbEpy 19.0 81.0 48.1

C

4

F

9 0C 2

H

5 HFOC-494pcE3y 36.3 63.7 71.2 10 The near azeotropic refrigerant compositions and concentration ranges of the present invention are listed in Table 3. TABLE 3 15 Near Azeotropic Concentration Range Compounds (AIB) wt% Alwt% B

C

4

F

9 OC2H 5 /HFOC-245eaE 1-62/99-38

C

4

F

9 0C 2

H

5 /HFOC-254faE 1-67/99-33

C

4

F

9 0C 2 H/HFOC-263ebEPy 1-76/99-24

C

4

F

9

OC

2

H

5 /HFOC-272fbE3y 1-67/99-33

C

4

F

9

OC

2

H

5 /HFOC-494pcE3py 1-99/99-1 Additional compounds from the list in Table 1 may be added to the binary compositions of the present invention to form ternary or higher order compositions. The azeotropic or near azeotropic compositions of the present 20 invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal stabilizer such as nitromethane. The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant 6 WO 2005/068580 PCT/US2005/001510 composition by permitting one observe the fluorescence of the dye under an ultra-violet light at the point of a leak within a refrigeration or air conditioning system. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants. 5 By "ultra-violet" dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be 10 detected. Therefore, if refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning apparatus, the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, 15 naphthoxanthenes, fluoresceins, and derivatives or combinations thereof. Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 20 1,1,1-trifluoroalkanes. Hydrocarbon solubilizing agents of the present invention r comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon 25 solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon. Hydrocarbon ether solubilizing agents of the present invention 30 comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME). Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R'[(OR 2 )xOR 3 ]y, wherein: x is an integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen 35 and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and 7 WO 2005/068580 PCT/US2005/001510 alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. In the present polyoxyalkylene glycol 5 ether solubilizing agents represented by R 1

[(OR

2 )xOR 3 ]y: x is preferably 1 2; y is preferably 1; R 1 and R 3 are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms;

R

2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the 10 polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. The R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R 1 and

R

3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, 15 isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar@), R 1 and R 3 are preferably aliphatic hydrocarbon radicals having 1 20 to 4 carbon atoms, most preferably 1 carbon atom. The R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2 )x - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R 2 in one polyoxyalkylene glycol ether solubilizing agent 25 molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. 30 Representative R 1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R 1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from 35 polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3 trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals. 8 WO 2005/068580 PCT/US2005/001510 Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH 3

OCH

2

CH(CH

3 )O(H or OH 3 ) (propylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2

CH(CH

3

)O]

2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2

CH(CH

3 )O]3(H 5 or OH 3 ) (tripropylene glycol methyl (or dimethyl) ether),

C

2

H

5 0sCH 2

CH(CH

3 )O(H or C 2

H

5 ) (propylene glycol ethyl (or diethyl) ether),

C

2 HeO[CH 2

CH(CH

3 )1O] 2 (H or C 2

H

5 ) (dipropylene glycol ethyl (or diethyl) ether), C 2 HO0[CH 2

CH(CH

3

)O]

3 (H or 0 2

H

5 ) (tripropylene glycol ethyl (or diethyl) ether), C 3

H

7 0CH 2

CH(CH

3 )O(H or 0 3

H

7 ) (propylene glycol n-propyl 10 (or di-n-propyl) ether), C 3

HO

7 0[CH 2

CH(CH

3 )O]2(H or C 3

H

7 ) (dipropylene glycol n-propyl (or di-n-propyl) ether), C 3

HO

7 0[CH 2

CH(CH

3

)O]

3 (H or C 3

H

7 ) (tripropylene glycol n-propyl (or di-n-propyl) ether), C 4

H

9 0CH 2

CH(CH

3 )OH (propylene glycol n-butyl ether), C 4 H90[CH 2

CH(CH

3 )1O] 2 (H or C 4

H

9 ) (dipropylene glycol n-butyl (or di-n-butyl) ether), C 4

H

9 0[CH 2

CH(CH

3 )O]3(H 15 or C 4

H

9 ) (tripropylene glycol n-butyl (or di-n-butyl) ether),

(CH

3

)

3

COCH

2

CH(CH

3 )OH (propylene glycol t-butyl ether),

(CH

3

)

3

CO[CH

2 CH(CH3)O] 2 (H or (CH 3

)

3 ) (dipropylene glycol t-butyl (or di-t butyl) ether), (CH 3

)

3

CO[CH

2

CH(CH

3

)O]

3 (H or (CH 3

)

3 ) (tripropylene glycol t butyl (or di-t-butyl) ether), CsHjOCH 2

CH(CH

3 )OH (propylene glycol n 20 pentyl ether), C 4

H

9 0CH 2

CH(C

2 He)OH (butylene glycol n-butyl ether),

C

4 HgO[CH 2

CH(C

2

H

5

)O]

2 H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C 2 HsC(CH 2 0(CH 2

)

3

CH

3

)

3 ) and trimethylolpropane di-n-butyl ether (C 2

H

5

C(CH

2 0C(CH 2

)

3

CH

3

)

2

CH

2 OH). Amide solubilizing agents of the present invention comprise 25 those represented by the formulae R'CONR 2

R

3 and cyclo-[R 4

CON(R

5 )-], wherein R 1 , R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 30 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R 1 , R 2 , R 3 and R 5 35 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In 9 WO 2005/068580 PCT/US2005/001510 general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 3 , and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the 5 aforementioned molecular weight limitations. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative

R

1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, 10 nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents are those wherein R 4 in the aforementioned formula cyclo-[R4CON(R)- ] may be represented by the hydrocarbylene radical (CR 6 R 7 )n, in other words, the formula: cyclo

[(CR

6

R

7 )nCON(R 5 )-] wherein: the previously-stated values for molecular 15 weight apply; n is an integer from 3 to 5; R 5 is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1"3 . In the lactams represented by the formula: cyclo-[(CR 6 R 7 )nCON(R 5 )-], all R 6 and

R

7 are preferably hydrogen, or contain a single saturated hydrocarbon 20 radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones. Representative amide solubilizing agents include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5 25 methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1 hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1 pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1 butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5 30 methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide. Ketone solubilizing agents of the present invention comprise ketones represented by the formula R 1

COR

2 , wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon 35 radicals having from I to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R 1 and R 2 in said ketones are preferably independently selected from 10 WO 2005/068580 PCT/US2005/001510 aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R 1 and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, 5 for example, cyclopentanone, cyclohexanone, and cycloheptanone.

R

1 and R 2 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R 1 and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, 10 radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non 15 hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R 1 and

R

2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula

R

1

COR

2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, 20 heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative ketone solubilizing agents include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, 25 hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3 heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4 decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone. 30 Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R'CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R 1 in said nitrile solubilizing agents is 35 preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass 11 WO 2005/068580 PCT/US2005/001510 units. R 1 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R 1 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, 5 which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in

R

1 , and the presence of any such non-hydrocarbon substituents and 10 heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R 1 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R 1 CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as 15 phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizing agents include but are not limited to: 1 cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1 cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1 cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane. 20 Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCIx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 25 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RCIx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 30 cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. Representative chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1 chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1 35 chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane. Ester solubilizing agents of the present invention comprise esters represented by the general formula R'CO 2

R

2 , wherein R 1 and R 2 12 WO 2005/068580 PCT/US2005/001510 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units. 5 Representative esters include but are not limited to:

(CH

3

)

2

CHCH

2 O0C(CH 2

)

2

-

4 OCOCH2CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial 07 alkyl acetate), "Exxate 10 800" (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate. Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [C]: 0 R, 0o O O RZ 'R 8 R R2 15

R

3

R

5

R

6 R4 RR 5

R

4 R6 [A] [B] [C] These lactones contain the functional group -CO 2 - in a ring of six (A), or 20 preferably five atoms (B), wherein for structures [A] and [B], R 1 through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each Ri though

R

8 may be connected forming a ring with another R 1 through R 8 . The lactone may have an exocyclic alkylidene group as in structure [C], 25 wherein R, through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R, though R 6 may be connected forming a ring with another R, through R 6 . The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from 30 about 80 to about 200 atomic mass units. Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 4. TABLE 4 13 WO 2005/068580 PCT/US2005OO1510 Additive Molecular Structure Molecular Molecular Formula Weight (am u (E,Z)-3-ethylidene-5-methyl- 0 0C 7

H

10 0 2 126 diliydro-furan-2-one (E,Z)-3-propylidene-5-methyl- 0 0 CsH 12 0 2 140 dihydro-furan-2-one (E,Z)-3-butylidene-5-methyl- 0 00 9

H

14 0 2 154 dihydro-furan-2-ofle (E,Z)-3-pentylidene-5-methyl- 0 0C 10

H

1 0 2 168 dihydro-furan-2-one - - ' (E,Z)-3-Hexylidene-5-methyl- 0 0 C 1 1 0 6 dihydro-furan-2-ofle jCjj 8 (E,Z)-3-Heptylldene-5-methyl- 0 0 0 12 Hzo 0 z 196 dihydro-furan-2-one ' (E,Z)-3-octylidene-5-methyl- 0 C1H20 1 dihydro-furan-2-one

C

3 2 0 1 (E,Z)-3-nonylidene-5-methyl- 0 0 C420 2 dihydro-furan-2-one

C

4 2 0 2 (E,Z)-3-decylidene-5-methyl- 0 0 dihydro-furan-2-one

C

5 2 0 3 (E,Z)-3-(3,5,5-trimethylhexylidefle)- 00 5-methyl-dilhydrofuran-2-ofle

C

14

HZ

4 0 2 224 (E,Z)-3-cyclohexylmethylidene-5- 0 0 methyl-dihydrofuran-2-one C \' C,2.H,802 194 gamma-octalactofle 0 0 CaH1 4 0 2 142 gamma-nonalactone 0 C91H16Oz 156 gamma-decalactone 0 0 CiolH 18 0 2 170 gamma-undecalactone 0 0 Cj20 8 gamma-dodecalactone 0 0

C

12 -120 2 198 3-hexyldihydro-furan-2-one 0 ilia17 3-heptyldihydro-furan-2-one IHo218 114 WO 2005/068580 PCT/US2005/001510 cis-3-ethyl-5-methyl-dihydro-fu ranl- 0 2-one

C

7

H

12 0 2 128 0 cis-(3-propyl-5-methyl)-dihydro- 0 furan-2-one CcH 14 0 2 142 0 cis-(3-butyl-5-rnethyl)-dliydro-0 furan-2-one 0 9

H

16 0 2 156 0 cis-(3-pentyl-5-methyl)-dihydrO furan-2-one

C

10

H

18 0 2 170 0 cis-3-hexyl-5-methyl-dihydro-furafl-18 2-one Ci20 8 0 furan-2-one C1 2

H

2 22 198 0 cis-3-octyl-5-methyl-dihydro-fu ran- 0 2-one

C

13

H

24 0 2 212 0 cis-3-(3,5,5-trimethylhexyl)-5-0 methyl-dihydro-furan-2-one 0C 14

H

26 0 2 226 cis-3-cyclohexylmethyl-5-methyl- 0 dihydro-furan-2-one AO C 12

H

20 0 2 196 5-methyi-5-hexyl-dihydro-,furafl-2- 0 one

CIIH

20 0 2 184 0 5-methyl-5-octyl-dihydro-furan-2- 0 one

C

13

H

24 0 2 212 Hexahydro-isobenzofuran-1 -one H 0 CaH 12 0 2 140 delta-decalactone aC 10 Hiu0 2 170 o o delta-undecalactone

CI

1

H

2 o0 2 184 0 0 delta-dodecalacone

C

12 H22O 2 198 0 0 15 WO 2005/068580 PCT/US2005/001510 mixture of 4-hexyl-dihydrofuran-2- 0 one and 3-hexyl-dihydro-furan-2- coHO 1 8 0 2 170 oneo 7L Oj Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40 0 C. For instance, gamma undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl 5 5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40 0 C. Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. provisional patent application 10/910,495 (inventors being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004, incorporated herein by reference. 10 Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R 1

OR

2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms;

R

2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of 15 from about 100 to about 150 atomic mass units. Representative R 1 aryl radicals in the general formula R 1

OR

2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R 2 aliphatic hydrocarbon radicals in the general formula R'OR 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative 20 aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether. Fluoroether solubilizing agents of the present invention comprise those represented by the general formula R'OCF 2

CF

2 H, wherein 25 R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C 8

H

17 0CF 2

CF

2 H and C 6

H

13

OCF

2

CF

2 H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may 30 not be the same fluoroether. 1,1,1-Trifluoroalkane solubilizing agents of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF 3

R

1 , wherein R' is selected from aliphatic and alicyclic 16 WO 2005/068580 PCT/US2005/001510 hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1 trifluoroalkane solubilizing agents include but are not limited to: 1,1,1 trifluorohexane and 1,1,1-trifluorododecane. 5 Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone 10 and a polyoxyalkylene glycol ether. In the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight 15 percent to about 0.25 weight percent. Solubility of these UV fluorescent dyes in refrigerants may be poor. Therefore, methods for introducing these dyes into the refrigeration or air conditioning apparatus have been awkward, costly and time consuming. US patent no. RE 36,951 describes a method, which utilizes a 20 dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are 25 described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration or air conditioning apparatus. The present invention relates to compositions including UV fluorescent dye, which may 30 be introduced into the system directly in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing refrigerant even at low temperatures while maintaining the dye in solution. In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about I to about 50 weight 35 percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant. In the compositions of 17 WO 2005/068580 PCT/US2005/001510 the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 5 weight percent. Optionally, commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability. These additives are known within the field of refrigeration, and include, but are not limited 10 to, anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,. In general, these additives are present in the inventive compositions in small amounts relative to the overall composition. Typically concentrations of from less than about 0.1 weight percent to as 15 much as about 3 weight percent of each additive are used. These additives are selected on the basis of the individual system requirements. These additives include members of the triaryl phosphate family of EP (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn 20 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and 25 asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides. 30 Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d 35 limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight 18 WO 2005/068580 PCT/US2005/001510 based on the combined weight of odor masking agent and solubilizing agent. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet 5 fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus. The method comprises introducing the refrigerant or heat transfer fluid composition into the refrigeration or air conditioning apparatus. This may be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a 10 solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and and UV fluorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition is may be used in the refrigeration or air 15 conditioning apparatus. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet fluorescent dye to detect leaks. The presence of the dye in the compostions allows for detection of leaking refrigerant in the refrigeration 20 or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the operation of the apparatus. The method comprises providing the composition comprising 25 refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a sutiable means for detecting the UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as 30 a "black light" or "blue light". Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. Once the ultra-violet fluorescent dye containing composition has been introduced to the refrigeration or air conditioning apparatus and has been allowed to circulate throughout the system, a leak can be found by shining 35 said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point. 19 WO 2005/068580 PCT/US2005/001510 The present invention further relates to a method of using the compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter 5 condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter evaporating said composition. Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes 10 through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector, and air. Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A 15 vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. 20 The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the 25 higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified as reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending 30 on the mechanical means to compress the fluid, or as positive displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed. Either positive displacement or dynamic compressors may be 35 used in the present inventive process. A centrifugal type compressor is the preferred equipment for the present refrigerant compositions. 20 WO 2005/068580 PCT/US2005/001510 A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it 5 radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is a stage of the compressor. Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the 10 volume of refrigerant to be handled. The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure. Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities. 15 Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero. A positive displacement compressor can build up a pressure, which is limited only by the 20 volumetric efficiency and the strength of the parts to withstand the pressure. Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no 25 positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is 30 determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity. Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine. A centrifugal 35 compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-1 1) or 1,2,2-trichlorotrifluoroethane

(CFC

113). 21 WO 2005/068580 PCT/US2005/001510 Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters. 5 A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a 10 compression ratio of about 4 to 1; that is, the absolute discharge pressure can be four times the absolute suction pressure. An example of a two stage centrifugal compressor system, in this case for automotive applications, is described in US 5,065,990, incorporated herein by reference. 15 The compositions of the present invention suitable for use in a refrigeration or air conditioning apparatus employing a centrifugal compressor are:

C

4

F

9

OC

2

H

5 and 1-(difluoromethoxy)-1,2,2-trifluoroethane;

C

4

F

9 0C 2

H

5 and 1-difluoromethoxy-2,2-difluoroethane; 20 C 4

F

9 0C 2

H

5 and 2-methoxy-1,1,2-trifluoroethane; 0 4

F

9 0C 2

H

5 and 1,1-difluoro-2-methoxyethane; and

C

4

F

9

OC

2

H

5 and 1-(1,1,2,2-tetrafluoroethoxy)propane. These above-listed compositions are also suitable for use in a multi-stage centrifugal compressor, preferably for a two-stage centrifugal compressor 25 apparatus. The compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers 30 and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems. The compositions of the present invention may additionally be 35 used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers. 22 WO 2005/068580 PCT/US2005/001510 Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. The low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design 5 may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger. 10 In addition to a two-stage or other multi-stage centrifugal compressor apparatus, compositions of the present invention that are suitable for use in a refrigeration or air conditioning apparatus employing a single slab/single pass heat exchanger are selected from the group consisting of: 15 C 4

F

9 0C 2

H

5 and 1-(difluoromethoxy)-1,2,2-trifluoroethane;

C

4

F

9 0C 2

H

5 and 1-difluoromethoxy-2,2-difluoroethane;

C

4

F

9 0C 2

H

5 and 2-methoxy-1,1,2-trifluoroethane;

C

4

F

9

OC

2

H

5 and 1,1-difluoro-2-methoxyethane; and

C

4

F

9 0C 2

H

5 and 1-(1,1,2,2-tetrafluoroethoxy)propane. 20 The compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pump as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the 25 engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high 30 driving speeds is taken into account, the advantage of these low pressure systems becomes even greater. Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal equipment. 35 The present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present 23 WO 2005/068580 PCT/US2005/001510 invention in the vicinity of a body to be cooled, and thereafter condensing said compositions. The present invention further relates to a process for producing heat comprising condensing the compositions of the present invention in 5 the vicinity of a body to be heated, and thereafter evaporating said compositions. The present invention further relates to a process for transfer of heat from a heat source to a heat sink wherein the compositions of the present invention serve as heat transfer fluids. Said process for heat 10 transfer comprises transferring the compositions of the present invention from a heat source to a heat sink. Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer 15 fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids 20 as well. A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a 25 supermarket, building spaces requiring air conditioning, or the passenger compartment of an automobile requiring air conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink. 30 EXAMPLES EXAMPLE 1 24 WO 2005/068580 PCT/US2005/001510 Impact of Vapor Leakage A vessel is charged with an initial composition at a specified temperature, and the initial vapor pressure of the composition is 5 measured. The composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. The results are summarized in Table 4 below. 10 TABLE 4 After 50% After 50% Compounds Initial Initial Leak Leak Delta wt% A/ wt% B Psia kPa Psia kPa P %

C

4 F9OC 2

H

5 /HFOC-245eaE (52.7 oC) 11.9/88.1 14.67 101.15 14.67 101.15 0.0% 1/99 14.57 100.46 14.57 100.46 0.0% 0/100 14.55 100.32 14.55 100.32 0.0% 40/60 14.21 97.98 13.89 95.77 2.3% 60/40 13.28 91.56 12.09 83.36 9.0% 61/39 13.21 91.08 11.96 82.46 9.5% 62/38 13.14 90.60 11.83 81.57 10.0% 100/0 6.61 45.57 6.61 45.57 0.0%

C

4

F

9 0C 2

H

5 /HFOC-254faE (54.0 OC) 26.0/74.0 14.72 101.49 14.72 101.49 0.0% 10/90 14.52 100.11 14.43 99.49 0.6% 1/99 14.13 97.42 14.10 97.22 0.2% 0/100 14.07 97.01 14.07 97.01 0.0% 60/40 14.00 96.53 13.17 90.80 5.9% 67/33 13.58 93.63 12.25 84.46 9.8% 100/0 6.93 47.78 6.93 47.78 0.0%

C

4

F

9 0C 2

H

5 /HFOC-263ebEl3y (54.0 °C) 40.2/59.8 14.71 101.42 14.71 101.42 0.0% 20/80 14.48 99.84 14.37 99.08 0.8% 10/90 14.19 97.84 14.06 96.94 0.9% 1/99 13.81 95.22 13.79 95.08 0.1% 0/100 13.76 94.87 13.76 94.87 0.0% 60/40 14.49 99.91 14.25 98.25 1.7% 75/25 13.90 95.84 12.73 87.77 8.4% 76/24 13.84 95.42 12.53 86.39 9.5% 100/0 6.93 47.78 6.93 47.78 0.0% 25 WO 2005/068580 PCT/US2005/001510

C

4

F

9 0C 2

H

5 /HFOC-272fbEpy (48.1 oC) 19.0/81.0 14.70 101.35 14.70 101.35 0.0% 10/90 14.66 101.08 14.65 101.01 0.1% 1/99 14.52 100.11 14.52 100.11 0.0% 0/100 14.50 99.97 14.50 99.97 0.0% 40/60 14.51 100.04 14.36 99.01 1.0% 60/40 13.91 95.91 13.08 90.18 6.0% 67/33 13.52 93.22 12.17 83.91 10.0% 100/0 5.57 38.40 5.57 38.40 0.0%

C

4

F

9

OC

2

H

5 /HFOC-494pcEpy (71.2 oC) 36.3/63.7 14.72 101.49 14.72 101.49 0.0% 20/80 14.64 100.94 14.62 100.80 0.1% 10/90 14.51 100.04 14.49 99.91 0.1% 1/99 14.35 98.94 14.34 98.87 0.1% 0/100 14.33 98.80 14.33 98.80 0.0% 60/40 14.52 100.11 14.47 99.77 0.3% 80/20 13.91 95.91 13.77 94.94 1.0% 90/10 13.37 92.18 13.23 91.22 1.0% 99/1 12.67 87.36 12.65 87.22 0.2% 100/0 12.58 86.74 12.58 86.74 0.0% The results show the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent has been removed is less then about 10 percent for compositions of the 5 present invention. This indicates compositions of the present invention are azeotropic or near-azeotropic. Where an azeotrope is present, the data show compositions of the present invention have an initial vapor pressure higher than the vapor pressure of either pure component. 26 WO 2005/068580 PCT/US2005/001510 EXAMPLE 2 Tip Speed to Develop Pressure Tip speed can be estimated by making some fundamental 5 relationships for refrigeration equipment that use centrifugal compressors. The torque an impeller ideally imparts to a gas is defined as T = m*(v2*r2-v1*rl) Equation 1 where 10 T = torque, N*m m = mass rate of flow, kg/s v2 = tangential velocity of refrigerant leaving impeller (tip speed), m/s r 2 = radius of exit impeller, m 15 vi = tangential velocity of refrigerant entering impeller, m/s r 1 = radius of inlet of impeller, m Assuming the refrigerant enters the impeller in an essentially radial direction, the tangential component of the velocity vi = 0, therefore 20 T = m*v2*r2 Equation 2 The power required at the shaft is the product of the torque and the rotative speed 25 P = T*w Equation 3 where P = power, W w = rotative speed, rez/s therefore, 30 P = T*w = m*v2*r2*w Equation 4 At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore 35 r2*w = v2 Equation 5 and P = m*v2*v2 Equation 6 27 WO 2005/068580 PCT/US2005/001510 Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression, 5 P = m*Hi*(1000J/kJ) Equation 7 where Hi = Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg. 10 Combining the two expressions Equation 6 and 7 produces, v2*v2 = 1000*Hi Equation 8 Although Equation 8 is based on some fundamental 15 assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants. Table 6 below shows theoretical tip speeds that are calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are: 20 Evaporator temperature 40.0,F (4.4C) Condenser temperature 110.0 0 F (43.3C) Liquid subcool temperature 10.0°F (5.50C) Return gas temperature 75.0°F (23.8 0 C) 25 Compressor efficiency is 70% These are typical conditions under which small turbine centrifugal compressors perform. TABLE 6 30 V2 rel Refrigerant C 4

F

9 0C 2

H

5 wt% B Hi Hi*0.7 Hi*0.7 V2 to CFC composition wt% Btullb Btu/lb KJ/Kg m/s 113 CFC-113 10.92 7.6 17.8 133.3 n/a

C

4

F

9

OC

2

H

5 plus (B): HFOC-245eaE 11.9 88.1 12.57 8.8 20.5 143.1 107% HFOC-254faE 26.0 74.0 13.75 9.6 22.4 149.6 112% HFOC- 40.2 59.8 14.45 10.1 23.5 153.4 115% 28 WO 2005/068580 PCT/US2005/001510 263ebEPy , HFOC- 19.0 81.0 16.41 11.5 26.7 163.5 123% 272fbEpy HFOC- 36.3 63.7 15.65 11.0 25.5 159.6 120% 494pcE3_ The Example shows that compounds of the present invention have tip speeds within about +/- 30 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design 5 changes. Most preferred compositions have tip speeds within about +/- 15 percent of CFC-113. EXAMPLE 3 Performance Data 10 Table 7 shows the performance of various refrigerants compared to CFC-113. The data are based on the following conditions. Evaporator temperature 40.0°F (4.4oC) Condenser temperature 110.0-F (43.30C) 15 Subcool temperature 10.0oF (5.50C) Return gas temperature 75.0 0 F (23.80C) Compressor efficiency is 70% TABLE 7 20 Compr Compr Evap Evap Cond Cond Disch Disch Refrigerant wt% wt% Pres Pres Pres Pres Temp Temp COP Capacity Capacity Composition AOCl B (Psia)(kPa) (Psia) (kPa) LF) (C) (Btulmin) (kW) CFC-113 2.7 19 12.6 88 156.3 69.1 4.18 14.8 0.26

C

4 17t0CgHs plus (B): HFOC- 11.9 88.1 2.2 15 11.7 81 160.3 71.3 4.34 15.6 0.27 245eaE HFOC-254faE 26.0 74.0 1.8 13 10.0 69 159.3 70.7 4.20 12.6 0.22 HFOC- 40.2 59.8 1.9 13 10.1 69 155.7 68.7 4.19 12.8 0.22 263ebE3py HFOC- 19.0 81.0 2.4 17 12.4 85 167.9 75.5 4.26 16.5 0.29 272fbEpy HFOC- 36.3 63.7 0.8 6 5.3 37 140.8 60.4 4.08 6.1 0.11 494pcEpy Data show the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions also have higher capacity or energy efficiency (COP) than CFC-113. 29

Claims (7)

1. A refrigerant or heat transfer fluid composition selected from the group consisting of: 5 C 4 F 9 0C 2 H 5 and 1-(difluoromethoxy)-1,2,2-trifluoroethane; C 4 F 9 0C2H 5 and 1-difluoromethoxy-2,2-difluoroethane; C 4 FO 9 0C 2 H 5 and 2-methoxy-1,1,2-trifluoroethane; C 4 F9OC 2 H 5 and 1,1-difluoro-2-methoxyethane; and C4F 9 0C 2 H 5 and 1-(1,1,2,2-tetrafluoroethoxy)propane. 10

2. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing (i) centrifugal compressor, or (ii) multi-stage centrifugal compressor, or (iii) a single slab/single pass heat exchanger, said composition comprising, said 15 composition selected from the group consisting of; C 4 F 9 0C 2 H 5 and 1 -(difluoromethoxy)-1,2,2-trifluoroethane; C 4 F 9 OC 2 H 5 and 1-difluoromethoxy-2,2-difluoroethane; C 4 F 9 0C 2 H 5 and 2-methoxy-1,1,2-trifluoroethane; C 4 F 9 0C 2 H 5 and 1,1-difluoro-2-methoxyethane; and 20 C 4 F 9 0C 2 H 5 and 1-(1,1,2,2-tetrafluoroethoxy)propane.

3. An azeotropic or near-azeotropic composition selected from the group consisting of: about 1 to about 62 weight percent C 4 F9OC 2 H 5 and about 99 25 to about 38 weight percent 1-(difluoromethoxy)-1,2,2 trifluoroethane; about 1 to about 67 weight percent C 4 FgOC 2 H 5 and about 99 to about 33 weight percent 1-difluoromethoxy-2,2-difluoroethane; about 1 to about 76 weight percent C 4 F 9 0C 2 H 5 and about 99 30 to about 24 weight percent 2-methoxy-1,1,2-trifluoroethane; about 1 to about 67 weight percent C 4 F 9 OC 2 H 5 and about 99 to about 33 weight percent 1,1-difluoro-2-methoxyethane; and about 1 to about 99 weight percent C 4 F 9 0C 2 H 5 and about 99 to about 1 weight percent 1-(1,1,2,2-tetrafluoroethoxy)propane. 35

4. An azeotropic composition selected from the group consisting of: 31 WO 2005/068580 PCT/US2005/001510

11.9 weight percent C 4 F 9 0C 2 H 5 and 88.1 weight percent 1 (difluoromethoxy)-1,2,2-trifluoroethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 52.7 oC;

26.0 weight percent 0 4 F 9 0C 2 H 5 and 74.0 weight percent 1 5 difluoromethoxy-2,2-difluoroethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 54.0 0C;

40.2 weight percent C 4 F 9 0C 2 H 5 and 59.8 weight percent 2 methoxy-1,1,2-trifluoroethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 54.0 oC; 10 19.0 weight percent C 4 F 9 OC 2 H 5 and 81.0 weight percent 1,1 difluoro-2-methoxyethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.1 oC; and 36.3 weight percent C 4 F 9 0C 2 H 5 and 63.7 weight percent 1 (1,1,2,2-tetrafluoroethoxy)propane having a vapor pressure of 15 about 14.7 psia (101 kPa) at a temperature of about 71.2 OC. 5. A process for producing refrigeration, said process comprising evaporating the composition of claim 1, 2, 3, or 4, in the vicinity of a body to be cooled, and thereafter condensing said composition. 20 6. A process for producing heat, said process comprising condensing the composition of claim 1, 2, 3, or 4 in the vicinity of a body to be heated, and thereafter evaporating said composition. 25 7. A method of using the compositions of claim 1, 2, 3, or 4, for heat transfer, said method comprising transferring said composition from a heat source to a heat sink. 8. The composition of claim 1, further comprising at least one ultra 30 violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dyes and combinations thereof. 35 9. The composition of claim 2, 3, or 4 further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, 32 WO 2005/068580 PCT/US2005/001510 phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dyes, and combinations thereof. 10. The composition of claim 8, further comprising at least one 5 solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and 1,1,1-trifluoroalkanes; and wherein the refrigerant and solubilizing agent are not the same compound. 10 11. The composition of claim 10, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R'[(OR 2 )xOR]y, wherein: xis an integer from 1 to 3; y is an 15 integer from 1 to 4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals 20 having from 1 to 6 carbon atoms; at least one of R 1 and R 3 is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R 1 'CONR 2 R 3 and cyclo 25 [R4CON(R 5 )-], wherein R 1 , R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon 30 atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R 1 COR 2 , wherein R 1 and R 2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and 35 wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; 33 WO 2005/068580 PCT/US2005/001510 d) nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic 5 mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular 10 weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R'OR 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl 15 , ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanes represented by the formula CF 3 R', wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; 20 i) hydrofluoroethers represented by the formula R'OCF 2 CF 2 H, wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; and j) lactones represented by structures [B], [C], and [D]: O 00 R 1 R7 R : Rs85 R3 R5 25 R 3 R P 4 R6 R 4 R [B] [C] [D] wherein, R 1 through R 8 are independently selected from 30 hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and k) esters represented by the general formula R'CO 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, 34 WO 2005/068580 PCT/US2005/001510 saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units. 5 12. A method for using the composition of claim 10, said method comprising: introducing the composition into a compression refrigeration or air conditioning apparatus by (i) dissolving the ultraviolet fluorescent dye in the refrigerant composition of heat transfer fluid in the presence of the solubilizing agent, and introducing the combination into said 10 compression refrigeration or air conditioning apparatus or (ii), combining solubilizing agent and and UV flurorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. 15 13. A method for using the composition of claim 8 or 10 in a compression refrigeration or air conditioning apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus. 20 14. A method of using the composition of claim 8 or 10, said method comprising: (i) producing refrigeration by evaporating said composition 25 in the vicinity of a body to be cooled and thereafter condensing said composition; or (ii) producing heat by condensing said composition in the vicinity of the body to be heated and thereafter evaporation said composition. 30 15. The composition of claim 1, 2, 3 or 4 further comprising a thermal stabilizer or odor masking agent. 16. The composition of claim 15 wherein said thermal stabilizer is 35 nitromethane. 35 WO 2005/068580 PCT/US2005/001510 17. A method of using the composition of claim 3, wherein said method comprises, producing heat or refrigeration in a refrigeration or air conditioning system employing a multi-stage centrifugal compressor. 5 18. The method of claim 17 wherein said multi-stage compressor is a two-stage centrifugal compressor. 36