Tracer-containing compositions and methods of making and use thereof

Abstract

A tracer-containing composition includes a thermal fluid and at least one tracer compound. The thermal fluid includes at least one refrigerant compound. The thermal fluid has at least about 99.5 wt% purity. The at least one tracer compound is present in an analytically detectable amount in the tracer-containing composition with the proviso that the thermal fluid is different from the tracer compound. The tracer-containing composition has at least 99.5 wt% purity. A method for verifying the source of a thermal fluid, a method for determining the occurrence of dilution of a composition including a thermal fluid, and a method of thermal control of an apparatus are also disclosed.

Description

TITLE OF THE INVENTIONTRACER-CONTAINING COMPOSITIONS AND METHODS OF MAKING AND USE THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63 / 535,783 filed on August 31, 2023, the disclosure of which is herein incorporated by reference in its entirety.FIELD OF THE INVENTION

[0002] The present disclosure relates to the fields of compression refrigeration and air conditioning. Specifically, the present disclosure relates to tracer-containing compositions including a thermal fluid and one or more tracer compounds, methods of making and using tracer-containing compositions, and methods of detecting tracer compounds in compositions to identify and verify their authenticity after leaving the custody of the original manufacturer or prior source.BACKGROUND OF THE INVENTION

[0003] Environmental concerns have led the refrigeration industry to high levels of consciousness around the responsible use of refrigerants. The refrigeration industry, as well as the society at large, benefits when everyone who manufactures, distributes, uses refrigerants, or services refrigeration and air conditioning equipment, uses all applicable measures to keep equipment operating at the highest achievable level of energy efficiency. This reduces the amount of energy consumed by the equipment. Higher than necessary energy consumption, as well as leakage of refrigerants, can contribute to unnecessary pollution of the atmosphere and waste of existing resources. This unnecessary waste also comes at a cost to the consumer for replacement of leaked refrigerant.

[0004] In response to environmental concerns, manufacturers of refrigerants have developed new refrigerant products that allow higher levels of energy efficiency when used in properly designed equipment. The new generation hydrofluorocarbon (HFC) refrigerants have less impact on the environment than older generationchlorinated refrigerants in the event that they inadvertently leak into the atmosphere. The HFC refrigerants have zero ozone depletion potential, and in general have less tropospheric climate, change potential than the refrigerants they replace. In addition, industry practices now mandate the elimination of leaks from most types of operating equipment and require that refrigerant gas be recovered from equipment when that equipment is taken out of service or is opened to allow service work to be performed.

[0005] While new high efficiency refrigerants and new responsible use policies are benefiting the environment, the benefit is not as great as it could be. In some instances, the recovered refrigerant gases are not properly reclaimed or recycled. The recovered refrigerant may be reinstalled back into other pieces of equipment without being properly reclaimed and cleaned to remove any harmful or energy efficiency reducing impurities which may have been introduced in handling or as a result of poorly performing or damaged equipment. The equipment into which this refrigerant is then introduced does not operate at peak efficiency and consumes more energy than necessary.

[0006] In addition, used refrigerant can be blended with virgin refrigerant, which generally results in a non-standard refrigerant gas composition. Similarly, used refrigerant can be re-packaged and sold as virgin refrigerant, without certification of purity and quality. These practices may result in increased atmospheric pollution and increased energy use, and places expensive refrigeration hardware at risk of being damaged.

[0007] In addition to negative environmental and equipment impact, there are economic losses to the refrigerant manufacturers and distributors. Refrigerant manufacturers make significant investments into the development of the quality new refrigerants products. Refrigerant distributors similarly have invested in equipment for the proper protection of refrigerants from contamination during packaging, storage, and distribution of refrigerants When refrigerants are diluted or blended with recovered refrigerants, and sold as virgin refrigerant, manufacturers and distributors do not receive the benefit of their investment.SUMMARY OF THE INVENTION

[0008] In some embodiments, a tracer-containing composition includes a thermal fluid and at least one tracer compound. The thermal fluid includes at least one refrigerant compound. The thermal fluid has at least about 98.5 wt%, about 99.0 wt%, most preferred at least about 99.5 wt% and less than 100wt% purity. The at least one tracer compound is present in an analytically detectable amount in the tracer-containing composition with the proviso that the thermal fluid is different from the tracer compound. The tracer-containing composition has at least about 99.5 wt% purity.

[0009] In some embodiments, a method for verifying the source of a thermal fluid includes (a) combining a quantity of a thermal fluid and at least one tracer compound to form a tracer-containing composition. The thermal fluid includes at least one refrigerant compound. The thermal fluid has at least about 99.5 wt% purity. The thermal fluid is different from the tracer compound. The tracer compound is present in an amount such that the tracer compound is analytically detectable in the tracercontaining composition. The tracer-containing composition has at least about 99.5 wt% purity. The method also includes (b) detecting the presence of the tracer compound in a thermal fluid selected for verification. The method further includes (c) comparing any detected quantity of the tracer compound to the quantity of the tracer compound in (a) to verify whether the selected thermal fluid corresponds to the tracer-containing composition from the source.

[0010] In some embodiments, a method for determining the occurrence of dilution of a composition including a thermal fluid includes (a) combining the thermal fluid and at least one tracer compound to form a tracer-containing composition. The thermal fluid includes at least one refrigerant compound. The thermal fluid has at least about 99.5 wt% purity. The thermal fluid is different from the tracer compound. The tracer compound is present in an amount such that the tracer compound is analytically detectable in the tracer-containing composition. The tracer-containing composition has at least about 99.5 wt% purity. The method also includes (b) detecting the presence of the tracer compound in a lesser quantity than originally added to the thermal fluid.

[0011] In some embodiments, a method of thermal control of a space includes producing refrigeration by evaporating a tracer-containing composition in the vicinity of a space to be cooled and thereafter condensing the tracer-containing composition or producing heat by condensing the tracer-containing in the vicinity of the space to be heated and thereafter evaporating the tracer-containing composition. The tracercontaining composition includes a thermal fluid and at least one tracer compound with the proviso that the thermal fluid is different from the at least one tracer compound. The thermal fluid includes at least one refrigerant compound and has at least about 99.5 wt% purity. The tracer compound is present in an amount such that the tracer compound is analytically detectable in the tracer-containing composition. The tracer-containing composition has at least about 99.5 wt% purity.DETAILED DESCRIPTION OF THE INVENTION

[0012] Provided are tracer-containing compositions and methods of making, identifying, and using tracer-containing compositions.

[0013] The compositions and methods described herein provide for the detection of tracer compounds in thermal fluids, which in turn, may alert the refrigeration industry to when dilution, adulteration, contamination, or other unauthorized practices have occurred with refrigeration / heating products.

[0014] The compositions and methods described herein provide a highly secure way to label a virgin thermal fluid product in a manner that does not compromise its performance or the product properties to any measurable extent, permit positive determination of when a refrigerant composition is diluted or altered in any way, or combinations thereof.

[0015] In some embodiments, a tracer-containing composition includes a thermal fluid and at least one tracer compound. The thermal fluid includes at least one refrigerant compound. The tracer compound is analytically detectable in the thermal fluid with the proviso that the thermal fluid is different from the tracer compound. In some embodiments, the thermal fluid is a virgin thermal fluid.

[0016] As used herein, “thermal fluid” refers to any refrigeration fluid or heating fluid used for heat transfer in a closed-loop system.

[0017] As used herein, “analytically detectable” refers to a tracer that may be detected by any analytical method capable of differentiating the tracer from the thermal fluid and / or capable of determining the quantity of tracer present.

[0018] As used herein, “virgin thermal fluid” refers to a thermal fluid composition having at least about 99.5 wt% purity that has not yet been used in a thermal fluid application.

[0019] In some embodiments, the presence of the analytically detectable amount of the tracer compound causes no significant difference in performance of the thermal fluid relative to the performance of the thermal fluid without the tracer compound. As used herein, “no significant difference” refers to less than a 1 % difference in any performance parameter of the thermal fluid. In some embodiments, the difference is less than 0.1 %.

[0020] Appropriate thermal fluids may be any common refrigeration / heating fluid used in the refrigeration industry (see http: / / ashrae.org / technical- resources / standards-and-guidelines / ashrae-refrigerant-designations as available on the filing date herewith; the disclosure of which is hereby incorporated by reference). Such thermal fluids may include hydrofluorocarbons (HFCs), Hydrofluoroolefins (HFOs), hydrochlorofluorocarbons (HCFCs), perfluorocarbons (PFCs), fluorocarbon ethers (HFEs), hydrocarbons (HCs), carbon dioxide (CO2), ammonia (NH3), or mixtures thereof.

[0021] In some embodiments, the refrigerant compound is a fluorocarbon refrigerant. Appropriate fluorocarbon refrigerants may include, but are not limited to, fluorocarbon refrigerants having 1-8 carbon atoms, containing at least one fluorine atom, optionally contain hydrogen, chlorine, and / or oxygen atoms, and have a normal boiling point of from -90°C to 80°C. In some embodiments, these fluorocarbon refrigerants are represented by the general formula CwF2w+2-x-yHxClyOz, where w is 1-6, x is 0-9, y is 0-3, z is 0-2, and 2w+2-x-y is a positive integer. In some embodiments, w is 1-6, x is 1-5, y is 0-1 , and z is 0-1 . In some embodiments, the fluorocarbon refrigerants are commercial products available from a number of sources such as The Chemours Company FC, LLC, Refrigerants, Wilmington, DE, 19801 , USA, or are available from custom chemical synthesis companies such as PCR Inc., P.O. Box 1466, Gainesville, Florida, 32602, USA, and additionally bysynthetic processes disclosed in publications such as Chemistry of Organic Fluorine Compounds, new edition, edited by Milos Hudlicky, published by Ellis Harwood- Prentice Hall Publishers, 1992.

[0022] Specific appropriate fluorocarbon refrigerants of such a formula may include, but are not limited to, CHCIF2 (HCFC-22), CHF3 (HFC-23), CH2F2 (HFC-32), CH3F (HFC-41), CF3CF3(FC-116), CHCIFCF3(HCFC-124), CHF2CF3(HFC-125), CH2CICF3(HCFC-133a), CHF2CHF2(HFC-134), CH2FCF3(HFC-134a), CCIF2CH3(HCFC-142b), CHF2CH2F (HFC-143), CF3CH3(HFC-143a), CHF2CH3(HFC-152a), CHF2CF2CF3(HFC-227ca), CF3CFHCF3(HFC-227ea), CHF2CF2CHF2(HFC-236ca), CH2FCF2CF3(HFC-236cb), CHF2CHFCF3(HFC-236ea), CF3CH2CF3(HFC-236fa), CH2FCF2CHF2(HFC-245ca), CH3CF2CF3(HFC-245cb), CHF2CHFCHF2(HFC- 245ea), CH2FCHFCF3(HFC-245eb), CHF2CH2CF3(HFC-245fa), CH2FCF2CH2F (HFC-254ca), CH3CF2CHF2(HFC-254cb), CH2FCHFCHF2(HFC-254ea), CH3CHFCF3(HFC-254eb), CHF2CH2CHF2(HFC-254fa), CH2FCH2CF3(HFC-254fb), CH3CF2CH3(HFC-272ca), CH3CHFCH2F (HFC-272ea), CH2FCH2CH2F (HFC- 272fa), CH3CH2CF2H (HFC-272fb), CH3CHFCH3(HFC-281ea), CH3CH2CH2F (HFC- 281fa), CHF2CF2CF2CF2H (HFC-338pcc), CF3CH2CF2CH3(HFC-365mfc), CF3CF2CF2OCHFCF3(heptafluoropropyl-1 ,2,2,2-tetrafluoroethyl ether), CF3CHFCHFCF2CF3(H FC-43- 10mee), C4FgOCH3, C4FgOC2Hs, or combinations thereof.

[0023] In some embodiments, the fluorocarbon refrigerant is represented by the general formula CwF2w-xHxOz, where w is 3 to 8, x is 0-17, z is 0 to 2, and 2w-x is a positive integer. Such fluorocarbon refrigerants may include unsaturated compounds and other functionalized fluorocarbons.

[0024] Specific appropriate refrigerant compounds of such a formula may include, but are not limited to, CF3(CF2)3CH=CH2(perfluorobutylethylene, PFBE), CF3CF2C(O)CF(CF3)2(perfluoroethylisopropylketone, PEIK), CF3C(O)CF(CF3)2(perfluoromethylisopropylketone, PMIK), or combinations thereof.

[0025] In some embodiments, the refrigerant compound is a hydrofluorocarbon or a hydrochlorofluorocarbon-based refrigerant compound. Specific appropriate hydrofluorocarbon or a hydrochlorofluorocarbon-based refrigerant compounds may include, but are not limited to, CHCIF2(HCFC-22), CHF3(HFC-23), CH2F2(HFC-32),CHCIFCF3(HCFC-124), CHF2CF3 (HFC-125), CHF2CHF2 (HFC-134), CH2FCF3 (HFC-134a), CF3CH3 (HFC-143a), CHF2CH3 (HFC-152a), CHF2CF2CF3 (HFC- 227ca), CF3CFHCF3 (HFC-227ea), CF3CH2CF3 (HFC-236fa), CHF2CH2CF3 (HFC- 245fa), CHF2CF2CF2CF2H (HFC-338pcc), CF3CHFCHFCF2CF3 (HFC-43-10mee), CF3(CF2)3CH=CH2(perfluorobutylethylene, PFBE), CF3CF2C(O)CF(CF3)2(perfluoroethylisopropylketone, PEIK), CF3C(O)CF(CF3)2 (perfluoromethylisopropylketone, PMIK), or combinations thereof.

[0026] In some embodiments, the thermal fluid is a zeotropic, azeotropic, or azeotrope-like blend thermal fluid. Appropriate blend thermal fluids may include, but are not limited to, HCFC-22 / HFC-152a / HCFC-124 (known by the American Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) designations R- 401A, R-401 B, and R-401 C), HFC-125 / HFC-143a / HFC-134a (known by the ASHRAE designation R-404A), HFC-32 / HFC-125 / HFC-134a (known by ASHRAE designations R-407A, R-407B, and R-407C), HCFC-22 / HFC-143a / HFC-125 (known by the ASHRAE designation R-408A), HCFC-22 / HCFC-124 / HCFC-142b (known by the ASHRAE designation R-409A), HFC-32 / HFC-125 (R-410A), or HFC-125 / HFC- 143a (known by the ASHRAE designation R-507). The compositions of certain blend thermal fluids can be found in “Factsheet 1 : Update on New Refrigerants Designations and Safety Classifications”, ASHRAE, April 2023 or at https: / / www.ashrae.org / technical-resources / standards-and-guidelines / ashrae- refrigerant-designations, which are incorporated by reference in their entirety herein.

[0027] In some embodiments, the thermal fluid includes up to about 10 weight percent of a non-fluorinated compound. Appropriate non-fluorinated compounds may include, but are not limited to, dimethyl ether or at least one C3 to C5 hydrocarbon, for example, propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2- dimethylpropane). Appropriate thermal fluids containing such C3 to C5 hydrocarbons may include, but are not limited to, azeotropic or azeotrope-like compositions of HCFC-22 / HFC-125 / propane (known by the ASHRAE designations R-402A and R-402B), HCFC- 22 / octafluoropropane / propane (known by the ASHRAE designations R-403A and R- 403B), octafluoropropane / HFC-134a / isobutane (known by the ASHRAE designation R-413A), HCFC-22 / HCFC-124 / HCFC-142b / isobutane (known by the ASHRAE designations R-414A and R-414B), HFC-134a / HCFC-124 / n-butane (known by theASHRAE designation R-416A), HFC-125 / HFC-134a / n-butane (known by the ASHRAE designation R-417A), HFC-125 / HFC-134a / dimethyl ether (known by the ASHRAE designation R-419A), and HFC-125 / HFC-134a / isobutane (known by ASHRAE designation R-422A).

[0028] In some embodiments, the tracer-containing composition is a virgin thermal fluid.

[0029] In some embodiments, a single refrigerant compound makes up at least 99.5 wt%, alternatively at least 99.6 wt%, alternatively at least 99.7 wt%, alternatively at least 99.8 wt%, alternatively at least 99.9 wt%, or any value, range, or sub-range therebetween, of the tracer-containing composition.

[0030] In some embodiments, a zeotropic, azeotropic, or azeotrope-like blend thermal fluid makes up at least 99.5 wt%, alternatively at least 99.6 wt%, alternatively at least 99.7 wt%, alternatively at least 99.8 wt%, alternatively at least 99.9 wt%, or any value, range, or sub-range therebetween, of the tracer-containing composition.

[0031] In exemplary embodiments, the presence of the tracer compound indicates the source of the tracer-containing composition. In some embodiments, the presence of a combination of tracer compounds indicates the source of the tracer-containing composition. As such, the selected tracer or combination of tracers is preferably not detectable in similar compositions from other sources.

[0032] In exemplary embodiments, the amount of the tracer or combination of tracers in the tracer-containing composition indicates a level of dilution of the tracercontaining composition from its original virgin thermal fluid state. As such, the relative amount of the tracer or combination of tracers in the tracer-containing composition preferably does not significantly change over time.

[0033] Appropriate tracer compounds for a tracer-containing composition that further includes a thermal fluid may include, but are not limited to, hydrocarbons, fluorocarbons, hydrofluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, fluoroethers, or combinations thereof.

[0034] Appropriate specific tracer compounds may include, but are not limited to, CFCb (CFC-11), CF2CI2 (CFC-12), CF3CI (CFC-13), CF2HCI (HCFC-22), CF3H(HFC-23), CH2FCI (HCFC-31), CH2F2(HFC-32), CH3CI (HCC-40), CH3F (HFC-41), CICF2CFCI2(CFC-113), CICF2CF2CI (CFC-114), CF3CF2CI (CFC-115), CF3CF3(FC- 116), CF3CHCI2(HCFC-123), CF3CHFCI (HCFC124), CF3CF2H (HFC-125), HCF2CF2H (HFC-134), CH3CH2F (HFC-161), C3HF5CI2 (HCFC-225), CF2=CFCI (CFO-1113), CF2=CF2(FO-1114), CF2=CHCI (HCFO-1122), CF2=CHF (HFO-1123), CHF=CHCI (HCFO-1131), CF3CCI=CHCF3(HCFO-1326), CF2=CCI2(CFO-1112a), CHF=CFCI (HCFO-1122a), CH2=CFCI (HCF0-1131a), CHF=CHCI (HCFO-1131 (E)), CH2=CHCI (HCO-1140), CF3CFCI2(CFC-114a), CF3CF2Br (115B1), CF3CF=CCI2(CFO-1214ya), CF3CF=CF2(FO-1216), CF3CF=CHCI (CFO-1224yd(Z)), CF3CF=CHF (HFO-1225ye(E)), CF3CF=CHF (HFO-1225ye(Z)), CF3CH=CF2(HFO- 1225zc), CH2=CCICFCI2(HCFO-1231xf), CH2=CCICF2CI (HCFO-1232xf), CF3CCI=CH2(HCFO-1233xf), CF3CH=CHCI (HCFO-1233zd(E)), CF3CF=CH2(HFO- 1234yf), CF3CH=CHF (HFO-1234ze(E)), CF3CH=CH2(HFO-1243zf), CF2CICF2H (HCFC-124a), C3H4F2(HFO-1252), CF3CF=CFCF3(FO-1318my), CF3CH2CI (HCFC- 133a), CF3CH2F (HFC-134a), CF3CH3(HFC-143a), CH3CF2H (HFC-152a), CF3CFCICF3(CFC-217ba), CF3CF2CF2CI (CFC-217ca), CF3CHFCF3(HCFC-227ea), CF3CF2CH2F (HFC-236cb), CF3CHFCF2H (HFC-236ea), CF3CH2CF3(HFC-236fa), CF3CFCICH3(HCFC-244bb), CF3CF2CH3(HFC-245cb), CF3CHFCH2F (HFC-245eb), CF3CH2CF2H (HFC-245fa), CF3CHFCH3(HFC-254eb), CF3CH2CH3(HFC-263fb), CF3CF2CHFCHFCF3(HFC-4310mee), CH3CH2CH2CH3(butane), C4H8(butylene), c- C4CI2F6 (dichlorohexafluorocyclobutane), CF3CF2I (pentafluoroethyl iodide), CH4(methane), CF3C=CH ((trifluormethyl)acetylene), or combinations thereof.

[0035] Tracer compounds or blends may be present in concentrations that are detectable by whichever analytical method is chosen. Preferably, the tracer concentration is chosen such that the quantity of tracer or tracer blend does not interfere with the performance of the thermal fluid. In some embodiments, the tracer compound or tracer blend is present in the tracer-containing composition at a total concentration of about 50 parts per million by weight (ppm) to about 5000 ppm, alternatively about 1000 ppm to about 4000 ppm, alternatively about 1000 ppm to about 2000 ppm, alternatively about 2000 ppm to about 3000 ppm, alternatively about 50 ppm to about 1000 ppm, alternatively about 50 ppm to about 500 ppm, alternatively about 100 ppm to about 300 ppm, alternatively about 100 ppm to about200 ppm, alternatively about 125 ppm to about 175 ppm, or any value, range, or subrange therebetween.

[0036] In some embodiments, individual tracer compounds are present at a concentration of about 1 ppm to about 5000 ppm, alternatively about 1000 ppm to about 4000 ppm, alternatively about 1000 ppm to about 2000 ppm, alternatively about 2000 ppm to about 3000 ppm, alternatively about 50 ppm to about 1000 ppm, alternatively about 50 ppm to about 500 ppm, alternatively about 100 ppm to about 300 ppm, alternatively about 100 ppm to about 200 ppm, alternatively about 125 ppm to about 175 ppm, alternatively about 1 ppm to about 100 ppm, alternatively about 5 ppm to about 80 ppm, or any value, range, or sub-range therebetween.

[0037] In some embodiments, the tracer compound is not analytically detectable in the thermal fluid as initially formed and is added to the thermal fluid in an analytically detectable amount to form the tracer-containing composition. A tracer compound or tracer blend may be added to a refrigerant compound or thermal fluid with any conventional equipment for blending refrigerants.

[0038] In some embodiments, the tracer compound is analytically detectable in the thermal fluid as initially formed. In such cases, an additional amount may optionally be added to reach a predetermined level of the tracer compound in the tracercontaining composition.

[0039] Single tracer compounds may be used in combination with a thermal fluid in a tracer-containing composition or multiple tracer compounds may be present in any combination and proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds.

[0040] In some embodiments, a method of making a tracer-containing composition includes combining an analytically detectable amount of tracer compound with a thermal fluid to make the tracer-containing composition.

[0041] The tracer-containing composition may be prepared by any convenient method to combine the desired amount of the individual components. In some embodiments, a method includes weighing the desired component amounts andthereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

[0042] In some embodiments, the refrigerant compound includes at least one of HFC-32, HFC-125, HFC-134a, and HFO-1234yf.

[0043] In some embodiments, the tracer compound includes at least one of HFC- 152a and HFO-1234yf.

[0044] In some embodiments, the refrigerant includes HFC-32, and the tracer compound includes at least one of HFC-152a and HFO-1234yf.

[0045] In some embodiments, the refrigerant includes HFC-125 and the tracer compound includes at least one of HFC-152a and HFO-1234yf.

[0046] In some embodiments, the refrigerant includes HFC-134a and the tracer compound includes at least one of HFC-152a and HFO-1234yf.

[0047] In some embodiments, the refrigerant includes HFO-1234yf and the tracer compound includes HFC-152a.

[0048] In some embodiments, the refrigerant compound includes HFC-32 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of CFC-12, HCFC-22, HFC-23, HCFC-31 , HCC-40, HFC-41 , HFC-134a, and HFC- 143a.

[0049] In some embodiments, the refrigerant compound includes HFC-32, and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HCFC-22, HFC-23, HCC-40, HFC-41, and HFC-143a.

[0050] In some embodiments, the refrigerant compound includes HFC-32, and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of CFC-12, HCFC-22, HFC-23, HCC-40, HFC-41, and HFC-143a.

[0051] In some embodiments, the refrigerant compound includes HFC-32, and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HFC-23, HCFC-31 , HFC-134a, HCFC-22, CFC-12, HCC-40 and HFC-143a.

[0052] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, HFC-134a, and HFC-143a.

[0053] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of CFC-13, HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

[0054] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

[0055] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HFC-23, HFC-143a, butane, and butylene.

[0056] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, and HFC-143a.

[0057] In some embodiments, the refrigerant compound includes HFC-125 and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HFC-23, CFC-115, HFC-143a, CFO-1113, and methane.

[0058] In some embodiments, the refrigerant compound includes HFC-134a and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1122, HCFO-1122a, HCFO-1131 , HCFO-1131a, and HFO-1243zf.

[0059] In some embodiments, the refrigerant compound includes HFC-134a and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1131, HCFO-1131 a, and HFO-1243zf.

[0060] In some embodiments, the refrigerant compound includes HFC-134a and the tracer blend includes at least one of HFC-152a and HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HCFO-1131 , HCFO-1131a, HCFO-1122

[0061] In some embodiments, the refrigerant compound includes HFO-1234yf and the tracer blend includes HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa, HFO-1225zc, HFO-1225ye(E), HFO-1225ye(Z), HFO- 1234ze(E), and HFO-1243zf.

[0062] In some embodiments, the refrigerant compound includes HFO-1234yf and the tracer blend includes HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa, HFO-1225zc, HFO-1225ye(E), HFO-1225ye(Z), HFO- 1234ze(E), and HFO-1243zf.

[0063] In some embodiments, the refrigerant compound includes HFO-1234yf and the tracer blend includes HFC-152a and at least one of CFC-12, HCFC-124, HFC- 134a, HCFC-244bb, HFC-245cb, HFC-254eb, HCFO-1131a, HCFO-1131(E), HCO- 1140, FO-1216, HCFO-1233xf, HFO-1234ze(E), and HFO-1243zf.

[0064] In some embodiments, a method of determining a source or a dilution of a tracer-containing refrigerant composition includes detecting the presence of a tracer compound in the tracer-containing refrigerant composition. In some embodiments, the detection includes determining an amount of the tracer and the occurrence of dilution, adulteration, or contamination of a refrigerant. In some embodiments, the detection includes determining the presence of the tracer and verifying the source of a refrigerant.

[0065] In some embodiments, a first tracer or combination of tracers may be analytically detected to confirm the source of the tracer-containing composition, whereas an amount of a second tracer or combination of tracers may be measured to confirm the level of dilution of the tracer-containing composition.

[0066] In the case where a dilution of the tracer-containing composition may have occurred, the tracer compound may be present in a lesser quantity than originally added to the thermal fluid. In some embodiments, analytical detection of the lesser quantity aids the refrigeration industry. Such detection is capable of alerting the industry to the occurrence of dilution, adulteration, or contamination. Therefore, in some embodiments, the tracer compound is added to the thermal fluid in an amount that is at least twice its detection limit, such as, for example, at least three times its detection limit, four times its detection limit, five times its detection limit, ten times its detection limit, or any value, range, or sub-range therebetween. Additionally,manufacturers, distributors and purchasers would be able to verify or authenticate the source or supplier of the thermal fluid by comparing any quantity of detected tracer to the quantity that was intentionally present in the thermal fluid at the source.

[0067] In some embodiments, gas chromatography (GC) is used to detect and quantify the tracer in the tracer-containing composition. Any GC detector may be used that is capable of detecting and preferably quantifying the tracer compound. Such detectors may include, but are not limited, to a flame ionization detector (FID), a thermal conductivity detector (TCD), an electron-capture detector (ECD), a photoionization detector (PID), an infrared detector (I RD), and a mass spectrometer (MS) detector, usually referred to as GC-MS when combined with a gas chromatograph. In some embodiments, another analytical method may be utilized which does not require the gas chromatographic separation prior to detection. Such other analytical methods include but are not limited to nuclear magnetic resonance (NMR) or infrared (IR) spectrometry.

[0068] When tracer-containing compositions are analyzed using gas chromatography, conditions capable of identifying and quantifying the tracer in the presence of the thermal fluid may be used. The GC column used for the analysis must be chosen so as to be capable of separating the tracer compound or components of the tracer blend from the thermal fluid. Both packed and capillary GC columns may be used. The preferred GC columns are those known to provide separation of fluorocarbon compounds from each other and classes of candidate tracer compounds of the present disclosure.

[0069] The packed GC columns that may be useful in methods of detection are from about 1 meter to about 12 meters in length. Generally, packed GC columns are constructed of stainless steel. The commercially available packed GC columns that may be useful in methods of detection include but are not limited to: porous polymer stationary phase, such as Porapak® Q or Porapak® T; silicone polymer stationary phases, such as SP®-1000 on Carbopack® B support or SP®-2100 (methyl silicone) on Supelcoport® support, perfluorinated polymer stationary phase, Fluorcol® on Carbopack® B support; and polyethylene glycol stationary phases, such as Carbowax® on Carbopack® C support. For those packed GC columns that are packed with a polymer coated support, the polymer loading may range from about0.1 % to about 10%. Packed GC columns listed here are available from Supelco (Bellefonte, PA).

[0070] Capillary GC columns which are found useful in methods of detection are available commercially. Capillary columns may vary in length from about 10 meters to about 105 meters but may also be longer if two or more columns are joined together, for example, 120 meters by joining two 60-meter capillary GC columns. The capillary GC columns that may be of use in methods of detection are generally constructed of fused silica tubing and vary in inner diameter (ID) from about 0.1 millimeter to about 0.53 millimeter. The stationary phase for the capillary GC columns is coated on the interior surface of the column and may vary in thickness from about 0.1 micrometer to about 5 micrometers. The stationary phases that may be of use in methods of detection, may include, but are not limited, to the commercially available liquid polymer phases: RTX®-1 ((Crossbond® 100% dimethyl polysiloxane), RT®-200 (Crossbond® trifluoropropylmethyl polysiloxane), RTX®-1301 (Crossbond® 6% cyanopropylphenyl / 94% dimethyl polysiloxane), RTX®-1701 (Crossbond® 14% cyanopropylphenyl / 86% dimethyl polysiloxane) from Restek Corporation (Bellefonte, PA). Porous layer open tubular (PLOT) capillary columns may also be useful in the present disclosure. Such PLOT capillary GC columns include, but are not limited to, the CP-PoraPLOT® Q (100% styrene divinylbenzene) column from Varian Chrompack (Middelburg, The Netherlands).

[0071] Temperature and pressure conditions for the GC analysis will vary depending upon the thermal fluid and the tracer being used in the composition. Cryogenic temperatures (sub-ambient, requiring liquid nitrogen, dry ice, or liquid carbon dioxide) may be used in order to provide separation of low boiling components (either thermal fluid or tracer compound(s)), when necessary.

[0072] In some embodiments, a method of using a tracer-containing refrigerant composition includes (i) producing refrigeration by evaporating the tracer-containing refrigerant composition in the vicinity of a space to be cooled and thereafter condensing the composition; or (ii) producing heat by condensing the tracercontaining refrigerant composition in the vicinity of the space to be heated and thereafter evaporating the composition.

[0073] In some embodiments, the tracer-containing refrigerant composition is a thermal fluid used for refrigeration or heating of a stationary structure, such as, for example, a building.

[0074] In some embodiments, the tracer-containing refrigerant composition is a blend thermal fluid used for refrigeration or heating of a non-stationary structure, such as, for example, an automotive.

[0075] Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, a liquid storage receiver, and an expansion device. A 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. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The high-pressure 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 high-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.OTHER EMBODIMENTS

[0076] Embodiment 1 : a tracer-containing composition comprising: a thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% purity; and at least one tracer compound, the at least one tracer compound being present in an analytically detectable amount in the tracer-containing composition with the proviso that the thermal fluid is different from the at least one tracer compound; wherein the tracer-containing composition has at least 99.5 wt% purity.

[0077] Embodiment 2: the composition of embodiment 1 , wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC-125, H FC- 134a, and HFO-1234yf.

[0078] Embodiment 3: the composition of embodiment 1 , wherein the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

[0079] Embodiment 4: the composition of embodiment 1 , wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC-125, and HFC-134a and the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

[0080] Embodiment 5: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a.

[0081] Embodiment 6: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-12, HCFC-22, HFC- 23, HCFC-31 , HCC-40, HFC-41, HFC-134a, and HFC-143a.

[0082] Embodiment 7: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCFC-22, HFC-23, HCC- 40, HFC-41, and HFC-143a.

[0083] Embodiment 8: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-12, HCFC-22, HFC- 23, HCC-40, HFC-41, and HFC-143a.

[0084] Embodiment 9: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40 and HFC-143a.

[0085] Embodiment 10: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, HFC-134a, and HFC-143a.

[0086] Embodiment 11 : the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

[0087] Embodiment 12: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCC-40, CFC- 115, HFC-134a, HFC-143a, and CFO-1113.

[0088] Embodiment 13: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HFC-143a, butane, and butylene.

[0089] Embodiment 14: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, and HFC-143a.

[0090] Embodiment 15: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, CFC-115, HFC- 143a, CFO-1113, and methane.

[0091] Embodiment 16: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC- 114a, HCFC-124, HFC-134, HFC-143a, HCFO-1122, HCFO-1122a, HCFO-1131 , HCFO-1131 a, and HFO-1243zf.

[0092] Embodiment 17: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC- 114a, HCFC-124, HFC-134, HFC-143a, HCFO-1131 , HCFO-1131a, and HFO- 1243zf.

[0093] Embodiment 18: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC- 114a, HCFC-124, HFC-134, HCFO-1131 , HCFO-1131a, HFO-1234ze, and HFO- 1243zf.

[0094] Embodiment 19: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO-1243zf.

[0095] Embodiment 20: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa, HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO-1243zf.

[0096] Embodiment 21 : the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of CFC-12, HCFC-124, HFC-134a, HCFC-244bb, HFC-245cb, HFC-254eb, HCFO-1131a, HCFO-1131(E), HCO-1140, FO-1216, HCFO-1233xf, HFO-1234ze(E), and HFO-1243zf.

[0097] Embodiment 22: the composition of embodiment 1 , wherein the at least one refrigerant compound comprises HFC-32 and the tracer-containing composition comprises at least 99.5 wt% HFC-32.

[0098] Embodiment 23: the composition of embodiment 22, wherein the at least one tracer compound comprises HFC-152a.

[0099] Embodiment 24: the composition of embodiment 1 , wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 1000 ppm.

[0100] Embodiment 25: the composition of embodiment 24, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 500 ppm.

[0101] Embodiment 26: the composition of embodiment 25, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 100 ppm to about 300 ppm.

[0102] Embodiment 27: the composition of embodiment 1 , wherein the at least one tracer compound comprises a first tracer compound selected to identify a source of the tracer-containing composition and a second tracer compound different from the first tracer compound and selected in an amount to identify a dilution level of the tracer-containing composition.

[0103] Embodiment 28: a method for verifying the source of a thermal fluid comprising: (a) combining a quantity of: (i) a thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% organic purity; and (ii) at least one tracer compound, with the proviso that the thermal fluid is different from the at least one tracer compound, to form a tracer-containing composition, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containing composition, wherein the tracer-containing composition has at least 99.5 wt% organic purity; (b) detecting the presence of the at least one tracer compound in a thermal fluid selected for verification; and (c) comparing any detected quantity of the at least one tracer compound to the quantity of the at least one tracer compound in (a) to verify whether the selected thermal fluid corresponds to the tracer-containing composition from the source.

[0104] Embodiment 29: a method for determining the occurrence of dilution of a composition comprising a thermal fluid, the method comprising: (a) combining (i) the thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% organic purity, and (ii) at least one tracer compound, with the proviso that the thermal fluid is different from the at least one tracer compound, to form a tracer-containing composition, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containing composition, wherein the tracer-containing composition has at least 99.5 wt% organic purity; and (b) detecting the presence of the at least one tracer compound in a lesser quantity than originally added to the thermal fluid.

[0105] Embodiment 30: a method of thermal control comprising: (i) producing refrigeration by evaporating a tracer-containing composition in the vicinity of a space to be cooled and thereafter condensing the tracer-containing composition; or (ii) producing heat by condensing the tracer-containing in the vicinity of the space to be heated and thereafter evaporating the tracer-containing composition; wherein the tracer-containing composition comprises a thermal fluid and at least one tracer compound with the proviso that the thermal fluid is different from the at least one tracer compound, the thermal fluid comprising at least one refrigerant compound and having at least 99.5 wt% organic purity, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containing composition, wherein the tracer-containing composition has at least 99.5 wt% organic purity.

[0106] Embodiment 31 : the method of any of embodiments 28-30, wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC-125, HFC-134a, and HFO-1234yf.

[0107] Embodiment 32: the method of any of embodiments 28-30, wherein the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

[0108] Embodiment 33: the method of any of embodiments 28-30, wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC-125, and HFC-134a and the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

[0109] Embodiment 34: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a.

[0110] Embodiment 35: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-12, HCFC-22, HFC-23, HCFC-31 , HCC-40, HFC-41 , HFC-134a, and HFC-143a.

[0111] Embodiment 36: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracercompound comprises HFC-152a or HFO-1234yf and at least one of HCFC-22, HFC- 23, HCC-40, HFC-41, and HFC-143a.

[0112] Embodiment 37: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-12, HCFC-22, HFC-23, HCC-40, HFC-41, and HFC-143a.

[0113] Embodiment 38: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40 and H FC- 143a.

[0114] Embodiment 39: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC- 23, CFC-115, HFC-134a, and HFC-143a.

[0115] Embodiment 40: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC- 23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

[0116] Embodiment 41 : the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

[0117] Embodiment 42: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, H FC- 143a, butane, and butylene.

[0118] Embodiment 43: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC- 23, CFC-115, and HFC-143a.

[0119] Embodiment 44: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, CFC-115, HFC-143a, CFO-1113, and methane.

[0120] Embodiment 45: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1122, HCFO-1122a, HCFO-1131 , HCFO-1131a, and HFO-1243zf.

[0121] Embodiment 46: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1131 , HCFO-1131a, and HFO-1243zf.

[0122] Embodiment 47: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HCFO-1131 , HCFO-1131a, HFO-1234ze, and HFO-1243zf.

[0123] Embodiment 48: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC- 245eb, HFC-245fa HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO- 1243zf.

[0124] Embodiment 49: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC- 245eb, HFC-245fa, HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO- 1243zf.

[0125] Embodiment 50: the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracercompound comprises HFC-152a and at least one of CFC-12, HCFC-124, HFC-134a, HCFC-244bb, HFC-245cb, HFC-254eb, HCFO-1131a, HCFO-1131(E), HCO-1140, FO-1216, HCFO-1233xf, HFO-1234ze(E), and HFO-1243zf.

[0126] Embodiment 51 : the method of any of embodiments 28-30, wherein the at least one refrigerant compound comprises HFC-32 and the tracer-containing composition comprises at least 99.5 wt% HFC-32.

[0127] Embodiment 52: the method of embodiment 51 , wherein the at least one tracer compound comprises HFC-152a.

[0128] Embodiment 53: the method of any of embodiments 28-30, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 1000 ppm.

[0129] Embodiment 54: the method of embodiment 53, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 500 ppm.

[0130] Embodiment 55: the method of embodiment 54, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 100 ppm to about 300 ppm.

[0131] Embodiment 56: the method of any of embodiments 28-30, wherein the at least one tracer compound comprises a first tracer compound selected to identify a source of the tracer-containing composition and a second tracer compound different from the first tracer compound and selected in an amount to identify a dilution level of the tracer-containing composition.

[0132] Embodiment 57: the method of embodiment 28, wherein the detecting comprises detecting by gas chromatography.

[0133] Embodiment 58: the method of embodiment 29, wherein the detecting comprises detecting by gas chromatography.

[0134] Embodiment 59: the method of embodiment 30, wherein the space is a stationary space.

[0135] Embodiment 60: the composition or method of any of the foregoing embodiments wherein the foregoing free of or substantially free of Group AFluorinated Substances. In one embodiment, as used herein, “Group A Fluorinated Substances” includes any substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / CI / Br / l attached to it); and (ii) meets the criterion for persistence in soil / sediment and water established in Annex XIII (Section 1.1.1) of the European Union’s REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html as accessed on May 2, 2023) and referenced in the Annex XV Restriction Report dated March 22, 2023, the disclosure of which is hereby incorporated by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea as accessed on May 2, 2023).

[0136] In another aspect of this embodiment, as used herein, “Group A Fluorinated Substances” includes any substance that has a Henry’s Law constant < 250 Pa*m3 / mol and contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / CI / Br / l attached to it).

[0137] In another aspect of this embodiment, Group A Fluorinated Substances include, but are not limited to, TFA.

[0138] The phrase "free of" as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas sample or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling the thermal fluid through water. Such methodologies are well known to those skilled in the art. The phrase "substantially free of" as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is> 0 wt.% and < 5 wt.%, or > 0 wt.% and < 4 wt.%, or > 0 wt.% and < 3 wt.%, or> 0 wt.% and < 2 wt.%, or > 0 wt.% and < 1 wt.%, and all values and ranges therebetween, when measured by gas chromatographic (GO) techniques, for example gas chromatography (GO) with a flame ionization or electron-capture detector, or GO coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatograph(IC) or ion chromatography massspectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography mass spectrometry (HPLC-MS) techniques. The TFA analytical standard may be used in either gas chromatography or ion chromatography and is available from, for example, Sigma Aldrich.

[0139] In an aspect of this embodiment, degradation products of compositions according to the present invention are free of or substantially free of Group A Fluorinated Substances. The phrase "free of" as used herein with respect to the formation of Group A Fluorinated Substances as degradation products of the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil / sediment and water produced during tropospheric degradation of the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by GO techniques, for example GO with a flame ionization or electron-capture detector or GC / MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. The phrase "substantially free of" as used herein with respect to the formation of Group A Fluorinated Substances by the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil / sediment and water produced during tropospheric degradation of the compositions is > 0% and < 5%, or > 0% and < 4%, or > 0% and < 3%, or > 0% and < 2%, or > 0% and < 1%, and all values and ranges therebetween, when measured by GC techniques, for example GC with a flame ionization or electron-capture detector or GC / MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.

[0140] In one aspect of this embodiment 60, the composition excludes greater than about 5 wt.% of HFO-1234yf. In one specific feature of this aspect, the composition comprises at least about 99.5 wt.% 32, a tracer comprising 152a and less than about 0.5wt.% HFO-1234yf.

[0141] While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any inventions or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features that are described in this specification in the context of separate implementations can also be implemented incombination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub-combination or variation of a sub-combination.

[0142] Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In certain circumstances, multitasking and parallel processing may be advantageous. Moreover, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.

[0143] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which example embodiments belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0144] While the disclosure has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosedherein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

CLAIMSWhat is claimed is:1 . A tracer-containing composition comprising: a thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% purity; and at least one tracer compound, the at least one tracer compound being present in an analytically detectable amount in the tracer-containing composition with the proviso that the thermal fluid is different from the at least one tracer compound; wherein the tracer-containing composition has at least 99.5 wt% purity.

2. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC- 125, HFC-134a, and HFO-1234yf.

3. The tracer-containing composition of claim 1 , wherein the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

4. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound is selected from the group consisting of HFC-32, HFC- 125, and HFC-134a and the at least one tracer compound is selected from the group consisting of HFC-152a, HFO-1234yf, and a combination thereof.

5. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a.

6. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCFC-31 , HFC-134a, HCFC-22, CFC-12, HCC-40, HFC-41 , HFC-134a, and HFC-143a.

7. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCFC-31 , HFC-134a, HCFC-22, CFC-12, HCC-40, HFC-41 , and HFC-143a.

8. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCFC-31, HFC-134a, HCFC-22, CFC-12,, HCC-40, HFC-41, and HFC-143a.

9. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-32 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40 and HFC- 143a.

10. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, HFC-134a, and HFC-143a.

11. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

12. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, HCC-40, CFC-115, HFC-134a, HFC-143a, and CFO-1113.

13. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, H FC- 143a, butane, and butylene.

14. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of CFC-13, HFC-23, CFC-115, and HFC-143a.

15. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-125 and the at least one tracercompound comprises HFC-152a or HFO-1234yf and at least one of HFC-23, CFC-115, HFC-143a, CFO-1113, and methane.

16. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1122, HCFO- 1122a, HCFO-1131, HCFO-1131a, and HFO-1243zf.

17. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HFC-143a, HCFO-1131, HCFO- 1131 a, and HFO-1243zf.

18. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFC-134a and the at least one tracer compound comprises HFC-152a or HFO-1234yf and at least one of HCC-40, CFC-114, CFC-114a, HCFC-124, HFC-134, HCFO-1131 , HCFO-1131a, HFO- 1234ze, and HFO-1243zf.

19. The tracer-containing composition of claim 1, wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO-1243zf.

20. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of HFC-236ea, HFC-245cb, HFC-245eb, HFC-245fa, HFO-1225ye(E), HFO-1225ye(Z), HFO-1234ze(E), and HFO-1243zf.

21. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises HFO-1234yf and the at least one tracer compound comprises HFC-152a and at least one of CFC-12, HCFC-124, HFC-134a, HCFC-244bb, HFC-245cb, HFC-254eb, HCF0-1131a, HCFO-1131 (E), HCO-1140, FO-1216, HCFO-1233xf, HFO-1234ze(E), and HFO-1243zf.

22. The tracer-containing composition of claim 1 , wherein the at least one refrigerant compound comprises H FC-32 and the tracer-containing composition comprises at least 99.5 wt% HFC-32.

23. The tracer-containing composition of claim 22, wherein the at least one tracer compound comprises HFC-152a.

24. The tracer-containing composition of claim 1 , wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 1000 ppm.

25. The tracer-containing composition of claim 24, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 50 ppm to about 500 ppm.

26. The tracer-containing composition of claim 25, wherein the at least one tracer compound is present in the thermal fluid in an amount ranging from about 100 ppm to about 300 ppm.

27. The tracer-containing composition of claim 1 , wherein the at least one tracer compound comprises a first tracer compound selected to identify a source of the tracer-containing composition and a second tracer compound different from the first tracer compound and selected in an amount to identify a dilution level of the tracer-containing composition.

28. A method for verifying the source of a thermal fluid, the method comprising:(a) combining a quantity of:(i) thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% purity; and(ii) at least one tracer compound, with the proviso that the thermal fluid is different from the at least one tracer compound, to form a tracer-containing composition, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containingcomposition, wherein the tracer-containing composition has at least 99.5 wt% purity;(b) detecting the presence of the at least one tracer compound in a thermal fluid selected for verification; and(c) comparing any detected quantity of the at least one tracer compound to the quantity of the at least one tracer compound in (a) to verify whether the selected thermal fluid corresponds to the tracer-containing composition from the source.

29. The method of claim 28, wherein the detecting comprises detecting by gas chromatography.

30. A method for determining the occurrence of dilution of a composition comprising a thermal fluid, the method comprising:(a) combining (i) the thermal fluid comprising at least one refrigerant compound, wherein the thermal fluid has at least 99.5 wt% organic purity, and (ii) at least one tracer compound, with the proviso that the thermal fluid is different from the at least one tracer compound, to form a tracer-containing composition, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containing composition, wherein the tracercontaining composition has at least 99.5 wt% purity; and(b) detecting the presence of the at least one tracer compound in a lesser quantity than originally added to the thermal fluid.

31. The method of claim 30, wherein the detecting comprises detecting by gas chromatography.

32. A method of thermal control of a space, the method comprising:(a) producing refrigeration by evaporating a tracer-containing composition in the vicinity of the space to be cooled and thereafter condensing the tracer-containing composition; or(b) producing heat by condensing the tracer-containing in the vicinity of the space to be heated and thereafter evaporating the tracer-containing composition; wherein the tracer-containing composition comprises a thermal fluid and at least one tracer compound with the proviso that the thermal fluid is different from the at least one tracer compound, the thermal fluid comprising at least one refrigerant compound and having at least 99.5 wt% purity, the at least one tracer compound being in an amount such that the at least one tracer compound is analytically detectable in the tracer-containing composition, wherein the tracer-containing composition has at least 99.5 wt% purity.

33. The method of claim 32, wherein the space is a stationary space.