WORLD INTELLECTUAL PROPERTY ORGANIZATION
`International Bureau
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`Q .
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`..-
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`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
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`(513 1"t9''“3fi°"3] P"‘t'3“t Classificatm" 7 ‘
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`(11) International Publication Number:
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`W0 00/56834
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`C09K 5/04
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`_
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`(43) International Publication Date:
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`28 September 2000 (2809.00)
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`(21) International Application Number:
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`PCT/US00/07546
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`(81) Designated States: JP, European patent (AT, BE, CH, CY, DE,
`DK, ES, Fl. FR, GB, GR, IE, IT, LU, MC, NL, PT, SE).
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`(22) International Filing Date:
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`22 March 2000 (2203.00)
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`(30) Priority Data;
`60/ 125,510
`Not furnished
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`22 March I999 (22.03.99)
`21 March 2000 (2l.03.00)
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`US
`Us
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`With international search report.
`Before the expiration of the time limit for amending the
`claims and to be republished in the event of the receipt of
`amendments.
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`Published
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`(71) Applicant: E.I. DU PONT DE NEMOURS AND COMPANY
`[US/US]; 1007 Market Street, Wilmington, DE 19898 (US).
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`(72) Inventors: BIVENS, Donald, Bernard; 210 West Locus Lane,
`Kennett Square, PA 19348 (US). MINOR, Barbara, Hav-
`iland; 233 Gieenhaven Drive, Elkton, MD 21921 (US).
`YOKOZEKI, Akimichi;
`I09 Congressional Drive, Apart-
`ment C, Wilmington, DE l9807 (US).
`
`(74) Agent: EDWARDS. Mark, A.; E.l. Du Pont dc Nemours and
`Company, Legal Patent Recotds Center, 1007 Market Street,
`Wilmington, DE 19898 (US).
`
`(54) Title: COMPOSITIONS OF DIFLUOROMETHANE, PENTAFLUOROETHANE, 1,1,l,2—'l"E'IRAFLUOROETHANE AND HY-
`DROCARBONS
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`(57) Abstract
`
`invention relates to a7eotrope-like compression refrigerant compositions consisting essentially of difluoromcthane
`The present
`(I-IFC—32), pentafluoroethane (HFC—I25), 1,l,l,2—tetrafluoroethane (HFC—|34a) and 0.5-5 weight percent of a hy(lroc.arbon selected from
`the group consisting of: n—butane; isobutane; n—iJutane and 2—methylbutanc; n—butane and n-pentane; isobutane and 2—mcthylbulanc; and
`isobutane and n——pentane.
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`Page 1 of 25
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`FOR THE PURPOSES OF INFORMATION ONLY
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`Austria
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`WO 00/56834
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`PCT/US00/07546“
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`TITLE
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`COMPOSITIONS OF DIFLUOROMETHANE, PENTAFLUOROETHANE,
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`1,1,1,2-TETRAFLUOROETHANE AND HYDROCARBONS
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`FIELD OF THE INVENTION
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`The present invention relates to azeotrope-like compositions consisting
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`essentially of difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and a
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`hydrocarbon selected from the group consisting of: n-butane; isobutane; n-butane
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`and 2—rnethylbutane; n—butane and n-pentane; isobutane and 2-methylbutane; and
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`isobutane and n-pentane.
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`BACKGROUND
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`In recent years it has been pointed out that certain kinds of fluorinated
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`hydrocarbon refrigerants released into the atmosphere may adversely affect the
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`stratospheric ozone layer. Although this proposition has not yet been completely
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`of certain chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCS)
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`under an international agreement. Accordingly, there is a demand for the
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`development of refrigerants that have a lower ozone depletion potential than
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`conventional CFC and HCFC-based refrigerants while still achieving an
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`acceptable performance in refrigeration applications. Hydrofluorocarbons (HFCS)
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`are gaining acceptance as replacements for CFCs and I-ICFCS as I-lFCs contain no
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`chlorine and therefore have zero ozone depletion potential.
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`Mineral oils and alkylbenzenes have been conventionally used as
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`lubricants in CFC-based refrigeration systems. However, the lack of solubility of
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`these lubricants in HFC-based refrigerants has precluded their use and
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`necessitated development and use of alternative lubricants for HFC-based
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`refrigeration systems, whichutilize polyalkylene glycols (PAGS) and polyol esters
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`(POES). A lubricant change from mineral oil or alkyl benzene to POE or PAG
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`lubricants (which increases expenses in the refrigeration indusrty) is required
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`when the HFC mixtures are used to replace CFC-based refrigerants. While the
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`PAGs and POES are suitable lubricants for HFC-based refrigeration systems, they
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`are extremely hygroscopic and can absorb several thousand ppm (parts per
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`million) of water on exposure to moist air. This absorbed moisture leads to
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`problems in the refrigeration system, such as formation of acids which cause
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`corrosion of the refrigeration system and formation of intractable sludges. In
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`contrast, mineral oils and alkylbenzenes are much less hygroscopic and have low
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`solubility, less than 100 ppm, for water. Additionally, PAG and POE lubricants
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`are considerably more expensive than the hydrocarbon lubricants, typically on the
`order ofthree to six times more expensive. Consequently, there is a need and an
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`opportunity to resolve this solubility problem so that the refrigeration industry
`may utilize mineral oil and alkylbenzene lubricants with HFC~based refrigerants.
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`In refrigeration apparatus, refrigerant may be lost during operation through
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`leaks in shaft seals, hose connections, soldered joints and broken lines. In
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`addition, the refrigerant may be released to the atmosphere during maintenance
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`procedures on refrigeration equipment. If the refrigerant is not a pure component
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`or an azeotropic or azeotrope-like composition, the refrigerant composition may
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`change when leaked or discharged to the atmosphere from the refrigeration
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`apparatus, which may cause the refrigerant remaining in the equipment to become
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`flammable or to exhibit unacceptable refrigeration performance. Accordingly, it
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`is desirable to use as a refrigerant a single fluorinated hydrocarbon or an
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`azeotropic or azeotrope-like composition which fractionates to a negilgible degree
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`upon leak from a refrigeration apparatus.
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`In refrigeration applications where the potential of fire or fire’s toxic
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`byproducts are a concern, it is desirable for refrigerant compositions to be
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`nonflammable in both liquid and vapor phases, when charging fresh refrigerant to
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`a system or after refrigerant has leaked from a system.
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`The refrigerants industry has strived to solve some of these problems, and
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`the following disclosures are evidence of such intent:
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`0 Powell et al. in World Intellectual Property Organization
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`international publication W0 9603473Al disclose a composition for use in a heat
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`transfer device of: (A) at least one hydrofluorocarbons selected from
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`difluoromethane and 1,1,1-trifluoroethane, (B) pentafluoroethane, (C) at least one
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`hydrocarbon, and optionally (D) at least one hydrofluorocarbon selected from
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`1 ,1,l ,2—tetrafluoroethane and 1 ,1 ,2,2-tetrafluoroethane.
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`0 Pearson in US patent number 5688432 discloses a refrigerant
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`comprising pentafluoroethane, tetrafluoroethane, a hydrocarbon selected from
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`isobutane and propane and optionally octafluoropropane.
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`o I-Iisanori et al. in Japan unexamined patent publication Hei 9-
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`25480 disclose a refrigerant composition of difluoromethane, 1,1,1,2—
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`tetrafluoroethane, pentafluoroethane and isobutane.
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`0 Kasuo in Europeanpatent application publication EP 0 659 862
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`10 Al discloses a refrigerant composition of difluoromethane, pentafluoroethane,
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`1 ,1, 1 ,2-tctrafluoroethane and n~pentane.
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`o Kazuo in Japan unexamined patent publication Hei 6-220430
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`disclose a refrigerant composition of difluoromethane, pentafluoroethane, 1,1,l,2—
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`tetrafluoroethane and n—pentane.
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`o Shiflett in US 5185094 discloses a refrigerant composition of
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`pentafluoroethane, difluoromethane and tetrafluoroethane.
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`0 Kinne et al. in DE 4226431 disclose a l,1,1,2-tetrafluoroethane
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`refrigerant composition containing 10-20 volume percent of a hydrocarbon.
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`o Bivens et al. in US 5616276 disclose a refrigerant composition of
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`chlorodifluoroethane, pentafluoroethane, and propane.
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`o Han et al. in W0 9715637 disclose refrigerant compositions of
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`incombustible halogenated compounds and combustible, essentially hydrocarbon,
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`compounds.
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`Accordingly, there is a need in the refrigeration industry for compositions
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`that are non-ozone depleting, nonflammable, and essentially non-fractionating
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`azeotrope—like compositions. Additionally, there is a need in the refrigeration
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`industry for compositions that offer improved return of conventional-refrigeration
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`lubricating oils from non-compressor to compressor zones in compression-
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`refrigeration apparatus, as well as superior refrigeration performance.
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`SUMMARY
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`The compositions of the present invention satisfy the aforementioned
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`needs confronting the refrigeration industry. The present compositions are useful
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`as refrigerants and in particular as HCFC-22 alternatives. Unlike compositions
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`containing propane and pcntane, compositions of the present invention are non-
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`flammable in both liquid and vapor phases, as intially formulated and during
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`leakage. The present invention relates to azeotrope-like compositions consisting
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`essentially of 1-19 weight percent difluoromethane (HFC«32), 25-60 weight
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`percent pentafluoroethane (HFC-125), 24-60 weight percent l,1,1,2-
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`tetrafluoroethane (I-IFC-13421) and 05-5 weight percent of a hydrocarbon, said
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`hydrocarbon selected from the group consisting of: n—butane; isobutane; n—butane
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`and 2-rnethylbutane; n—butane and n-pentane; isobutane and 2—methylbutane; and
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`isobutane and n-pentane.
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`DETAILED DESCRIPTION
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`The azeotrope-like compositions of the present invention consist
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`essentially of difluoromethane (HFC-32, CH2F2, normal boiling point of -S1 .7°C),
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`pentafluoroethane (HFC-125, CF3CHF2, normal boiling point of 485°C), 1,1,1,2-
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`tetrafluoroethane (HFC-134a, CF3CHF2_ normal boiling point of —26.1°C) and a
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`hydrocarbon selected from the group consisting of: n—butane (CH3CH2CI-IZCH3,
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`normal boiling point of -0.5°C); isobutane (CH(CH3)3, normal boiling point of -
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`l1.8°C); n—butane and 2-methylbutane (CH3CH2CH(CH3)2, normal boiling point
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`of 27.9°C); n—butane and n-pentane (CH3CH2CH2CH2CH3, normal boiling point of
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`359°C); isobutane and 2-methylbutane; and isobutane and n-pentane.
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`The azeotrope-like compositions of the present invention consist
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`essentially of 1-19 weight percent difluoromethane, 25-60 weight percent
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`pentafluoroethane, 24-60 weight percent 1,1,l,2~tetrafluoroethane and 0.5-5
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`weight percent of a hydrocarbon, said hydrocarbon selected from the group
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`consisting of: n—butane; isobutane; n—butane and 2-methylbutane; n—butane and n-
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`pentane; isobutane and 2-methylbutane; and isobutane and n-pentane. The
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`preferred azeotrope-like compositions of the present invention consist essentially
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`of 1~l5 weight percent difluoromethane, 30-50 weight percent pentafluoroethane,
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`30-50 weight percent l,1,1,2-tetrafluoroethane and 1-4 weight percent of the
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`aforementioned hydrocarbons. The most preferred azeotrope-like compositions of
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`the present invention consist essentially of 1-9 weight percent difluoromethane
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`Page 6 of 25
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`(HFC~32), 30-50 weight percent pentafluoroethane (HFC-125), 30—50 weight
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`percent 1,1,l,2-tetrafluoroethane (HFC-134a) and 1-4 weight percent of the
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`aforementioned hydrocarbons.
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`By azeotrope-like composition is meant a constant boiling, or substantially
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`constant boiling, liquid admixture of two or more substances that behaves as a
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`single substance. One way to characterize an azeotrope-like composition is that
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`the vapor produced by partial evaporation or distillation of the liquid has
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`substantially the same composition as the liquid from which it was evaporated or
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`distilled. Essentially, the admixture distills/refluxes without substantial
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`composition change. Another way to characterize an azeotrope—like composition
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`is that the bubble point vapor pressure and the dew point vapor pressure of the
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`composition at a particular temperature are substantially the same. Herein, a
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`composition is azeotrope-like if, after 50 weight percent of the composition is
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`removed such as by evaporation or boiling off, the difference in vapor pressure
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`between the original composition and the composition remaining after 50 weight
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`percent of the original composition has been removed is less than 10 percent.
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`By effective amount is meant the amount of each component of the
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`inventive compositions which, when combined, results in the formation of an
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`azeotrope-like composition. This definition includes the amounts of each
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`20
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`component, which amounts may vary depending on the pressure applied to the
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`composition so long as the azeotrope—like compositions continue to exist at the
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`different pressures, but with possible different boiling points. Therefore, effective
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`amount includes the amounts, such as may be expressed in weight percentages, of
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`each component of the compositions of the instant invention which form an
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`25
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`azeotrope-like compositions at temperatures or pressures other than as described
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`herein.
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`The azeotrope-like compositions of the present invention can be prepared
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`by any convenient method including mixing or combining effective amounts of
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`components. A preferred method is to weigh the desired component amounts and
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`30
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`thereafter combine them in an appropriate container.
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`A surprising result, and an important feature of the present compositions,
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`is that they remain nonflarnrnable in both the vapor and liquid phases before and
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`Page 7 of 25
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`Page 7 of 25
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`WO 00/56834
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`PCT/US00/07546
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`after the compositions leak from a container. Based on standard flammability test
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`method ASTM 681 at 100°C, the following flammability limits have been
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`determined:
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`5
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`Composition
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`Flammability Limit (Wt%)
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`HFC-125/I-IFC-32
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`57 % HFC-32
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`HFC—l34a/HFC—32
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`33 % HFC-32
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`HFC-125/n-butane
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`6 % n—butane
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`HFC-134a/n-butane
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`I 3 % n—butar1c
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`10
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`15
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`The data show compositions with a higher amount of HFC—l25 can
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`tolerate more hydrocarbon and still be nonflammable. Also, HFVC-32 is about 10
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`times less flammable than hydrocarbons. To give an indication of mixture
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`flammability, the following formula gives an approximation of the “total
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`equivalent hydrocarbon” (THE) present in mixtures that contain both HFC-32 and
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`hydrocarbons: TEH = HC + R3 2/10, where TEH = Total Equivalent Hydrocarbon
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`in weight percent, HC = weight percent hydrocarbon in a mixture, and R32 =
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`weight percent HFC—32 in a mixture. For the compositions of the present
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`invention, it is useful to relate the amount of HFC-125 in the mixture to
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`flammability because HFC—125 has some degree of flame suppression. Table 1
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`indicates the flammability limit of a mixture containing both I-IFC-32 and
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`hydrocarbons based on HFC-125 composition and TEH.
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`TABLE 1
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`Weight Percent HFC-125 in
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`Maximum Weight Percent
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`HFC—32/HFC-125/HFC—
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`TEH To Be Nonflammable
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`134a/HC Mixture
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`Page 8 of 25
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`Page 8 of 25
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`WO 00/56834
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`PCT/US00/07546
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`Additives known in the refrigerants field such as lubricants, corrosion
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`inhibitors, surfactants, stabilizers, anti-foam agents, dyes and other appropriate
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`materials may be added to, and used in the presence of, the present compositions
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`5
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`of the invention for a variety of purposes, provide that such additives do not have
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`an adverse influence on the present compositions for their intended application or
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`change the basic and novel characteristics of the present invention as claimed.
`Although the present specification is directed to use of the present
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`azeotrope-like compositions as compression refrigerants, the present compositions
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`10
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`may also find utility as cleaning agents, expansion agents for polyolefins and
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`polyurethanes (polymer foam blowing agents), aerosol propellants, heat transfer
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`media, gaseous dielectrics, power cycle working fluids, polymerization media,
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`particulate removal fluids, carrier fluids, buffing abrasive agents and displacement
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`drying agents.
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`15
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`EXAMPLES
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`Specific examples illustrating the present invention are given below.
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`Unless otherwise stated therein, all percentages are by weight.
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`20
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`EXAMPLE 1: Impact of Vapor Leakage on Compositional Change at 25°C of a
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`HFC-32, HFC-125, HFC-134a, n-butane and optionally 2-methylbutane or n-
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`pentane Composition
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`A vessel is charged to 90 volume % full with an initial composition of
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`I-IFC-32, HFC—125, HFC-134a, n-butane and optionally 2-methylbutane or n-
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`25
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`pentane at 25°C. The initial liquid and vapor compositions are measured by gas
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`chromatography. The composition is allowed to leak from the vessel, while the
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`temperature is held constant at 25°C, until 50 weight percent of the initial
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`composition is removed, at which time the liquid and vapor compositions
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`Page 9 of 25
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`Page 9 of 25
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`remaining in the vessel are again measured. The vessel is than allowed to
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`continue to leak until all the liquid is gone. In all cases, liquid was gone after
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`about 97wt% was removed. The results are summarized in Table 2 below. All
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`compositions are given in weight %.
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`5
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`TABLE 2
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`Initial
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`Initial
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`n-butane
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`TE“
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`2
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`.5
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`1 .6
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`re-
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`Liquid Vapor
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`OQ
` oc.a-——n
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`n—-»I\)
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`37.9
`52.4
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`48.8
`37.6
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`17.6
`78.7
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`1.9
`7.3
`11.0
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`17.7
`38.8
`49.2
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`80.3
`37.3
`52.9
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`1.0
`2.5 n .
`GO L;.)r—-
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`54.3
`29.0
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`3*’ \O
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`13.9
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`52.3
`28.3
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`5.5
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`69*
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`42.5
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`we U1
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`10.0
`45.0
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`42.5
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`L».3l\)
`Ullh
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`HFC—125
`HFC-134a
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`HFC-32
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`HFC-125
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`HFC-134a
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`propane
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`TE“
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`HFC-32
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`HFC—125
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`29.3
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`51.9
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`38.2
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`72.7
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`78.5
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`-1111
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`HFC-134a
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`42.5
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`n-«pentane
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`Page 10 of 25
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`Page 10 of 25
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`W
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`2.
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`0.5%
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`m I
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`-IFC-32
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`5.0
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`3.2
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`5.4
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`0.2
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`Iii
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`52.2
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`38.0
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`29.7
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`* Compositions are flammable based on TEH analysis
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`HMS
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`HFC-134a
`42.7
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`n-pentane
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`i When TEH values of this Example are compared to Table 1, results show
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`compositions of the precent invention are essentially nonflammable, initially and
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`as contents are completely leaked out of the container. Data also show addition of
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`a higher boiling hydrocarbon such as 2-methylbutane reduces initial vapor phase
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`flammability when compared to using only n-butane. Compositions containing
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`propane are flammable initially in the vapor phase and compositions containing n-
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`pentane become flammable in the liquid and/or vapor phases as liquid is removed.
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`Page 11 of 25
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`Page 11 of 25
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`EXAMPLE 2: Impact of Vapor Leakage on Compositional Change at 25°C of a
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`HFC-32, HFC—125, I-IFC—l 34a, isobutane and optionally 2—rnethy1butane or n-
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`pentane Composition
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`5
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`A vessel is charged to 90 volume % full with an initial composition of
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`HFC—32, HFC-125, I-IFC-134a, isobutane and optionally 2-methylbutane or n-
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`pentane at 25°C. The initial liquid and vapor compositions are measured by gas
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`chromatography. The composition is allowed to leak from the vessel, while the
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`temperature is held constant at 25°C, until 50 weight percent of the initial
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`composition is removed, at which time the liquid and vapor compositions
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`remaining in the vessel are again measured. The vessel is than allowed to
`continue to leak until all the liquid is gone. In all cases, liquid was gone after
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`about 97 wt% was removed. The results are summarized in Table 3 below. All
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`compositions are given in weight %.
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`1 5
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`TABLE 3
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` Liquid
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`Vapor
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`-FC-125-.0 55.3
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`30
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`Initial
`Initial
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`43
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` HFC-32
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`10.0
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`14.0
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`7.4
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`10.9
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`1
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`2 2
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`T
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`77.2
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`86.7
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`40.2
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`50.3
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`50.8
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`35.5
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`HFC-125
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`HFC-134a
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`47.0
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`40.5
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`55.7
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`27.3
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`Page 12 of 25
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`wo 00/56834
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`-FC-125-.5-54.2‘.0-.9-0‘.0
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`In
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`T -
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`:c—32—5.0-3.0“-5“-
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`1 1
`HFC-134a W 7.1
`55.9
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`05
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`1
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`5::
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`1.9
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`r—-
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`D—-‘
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`Ix)
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`isobutane
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`2-mbutane
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`29.2
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`'N
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`19.0
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`74.9
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`°‘
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`2'3
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`2'8
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`HFC-125
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`50
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`55.8
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`45 3
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`53.2
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`25.3
`I-IFC-134a
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`0.4
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`E1 0-5
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`When TEH values of this Example are compared to Table 1, results show
`compositions are essentially nonflammable, initially and as contents are
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`completely leaked out of the container. Data also show addition of a higher
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`5
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`boiling hydrocarbon such as n-pentane reduces initial vapor phase flammability
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`when compared to using only isobutane.
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`EXAMPLE 3: Impact of Vapor Leakage on Vapor Pressure at 25°C
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`A vessel is charged with an initial composition at 25°C, and the initial
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`10
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`vapor pressure of the composition is measured. The composition is allowed to
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`leak from the vessel while the temperature is held constant at 25°C until 50 weight
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`11
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`Page 13 of 25
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`Page 13 of 25
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`WO 00/56834
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`PCT/US00/07546
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`percent of the initial composition is removed, at which time the vapor pressure of
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`the composition remaining in the vessel is measured. The results are summarized
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`in Table 4 below.
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`5
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`TABLE 4
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`Initial
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`Pressure
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`(kPa)
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`1044
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`%Change
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`in
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`Pressure
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`8.3
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`Composition (Wt%)
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`HFC~32/HFC-125/HFC-134/nvbutane
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`1.0/60.0/34.0/5.0
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`19.0/56.5/24.0/0.5
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`9.0/46.0/42.5/2.5
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`5.0/34.0/60.0/1.0
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`16.0/57.0/24.0/3.0
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`19.0/25.0/51.0/5.0
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`10.0/45.0/42.5/2.5
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`HF C-32/HF C-125/HF C-
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`134a/isobutane
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`1.0/60.0/34.0/5.0
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`19.0/56.5/24.0/0.5
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`9.0/46.0/42.5/2.5
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`5.0/34.0/60.0/1.0
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`16.0/57.0/24.0/3.0
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`10.0/45.0/42.5/2.5
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`10.0/47.0/40.5/2.5
`HFC-32/HFC—125/HFC—1 34a/n-
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`1.0/60.0/34.0/0.5/4.5
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`butane/2-methylbutane
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`19.0/56.5/24.0/0.5/0.5
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`9.0/46.0/42.5/1.0/1.5
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`5.0/34.0/60.0/0.5/0.5
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`16.0/57.0/24.0/2.0/1.0
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`19.0/25.0/51.0/4.5/0.5
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`10.0/45.0/42.5/2.0/0.5
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`HFC-32/HFC-125/HFC-134a/n-
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`12
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`Page 14 of 25
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`Page 14 of 25
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`WO 00/56834
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`PCT/US00/07546
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`butane/n-pentane
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`1.0/60.0/34.0/0.5/4.5
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`19.0/56.5/24.0/0.5/0.5
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`5.0/34.0/60.0/0.5/0.5
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`19.0/25.0/51.0/4.5/0.5
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`10.0/45.0/42.5/2.0/0.5
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`HFC—32/HFC-125/HFC-
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`1.0/60.0/34.0/0.5/4.5
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`1 34a/isobutane/2-methylbutane
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`19.0/56.5/24.0/0.5/0.5
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`9.0/46.0/42.5/1.0/1.5
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`5.0/34.0/60.0/0.5/0.5
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`19.0/25.0/51.0/4.5/0.5
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`10.0/45.0/42.5/2.0/0.5
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`HFC-32/HFC-125/HFO
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`1.0/60.0/34.0/0.5/4.5
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`134a/isobutane/n-pentane
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`19.0/56.5/24.0/0.5/0.5
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`9.0/46.0/42.5/1.0/1.5
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`5.0/34.0/60.0/0.5/0.5
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`16.0/57.0/24.0/2.0/1.0
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`19.0/25.0/51.0/4.5/0.5
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`10.0/45.0/42.5/2.0/0.5
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`HFC-32/HFC-125/HFC—134a/propane
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`(10.0/45.0/42.5/2.5
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`1247
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`1096
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`8.7
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`7.8
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`5.9
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`9.1
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`6.1
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`10.0
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`8.4
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`The results of this Example show azeotrope-like compositions of the
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`present invention are present as after 50 wt% of an original composition is
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`removed, the vapor pressure of the remaining composition is changed by less than
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`about 10% of the vapor pressure of the original composition, at a temperature of
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`25°C. Reducing the amount of HFC-32 in the compositions may result in a more
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`azeotrope-like mixture. Compositions containing propane are not azeotrope-like.
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`EXAMPLE 4: Effect of Hydrocarbon Addition on Fractionation
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`13
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`Page 15 of 25
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`Page 15 of 25
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`wo 00/55334
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`PCTHJSOO/07546
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`A vessel is charged 90% full by volume with an initial composition at
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`25°C, and the initial vapor pressure of the composition is measured. The
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`composition is allowed to leak from the vessel, while the temperature is held
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`constant at 25°C until 50 weight percent of the initial composition is removed, at
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`which time the vapor pressure of the composition remaining in the vessel is
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`measured. The results are summarized in Table 5 below.
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`TABLE 5
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`Composition (Wt%)
`
`
`
`
`Initial
`Pressure
`
`
`
`
`
`
`Pressure After % Change in
`
`
`Pressure
`
`
`
`
`HFC-32/HFC-125/IIFC-134a
`
`
`(refrigerant “R407C”)
`
`
`(23/25/52)
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`HFC-32/HFC-125/HFC—
`
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`134a/n-butane (15/42/41 .5/1.5)
`HFC~32/HFC—125/HFC-
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`(1<Pa)
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`134a/n-butane (