US3470101A - Fluorinated hydrocarbon compositions - Google Patents
Fluorinated hydrocarbon compositions Download PDFInfo
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- US3470101A US3470101A US313643A US3470101DA US3470101A US 3470101 A US3470101 A US 3470101A US 313643 A US313643 A US 313643A US 3470101D A US3470101D A US 3470101DA US 3470101 A US3470101 A US 3470101A
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- 239000000203 mixture Substances 0.000 title claims description 83
- 229930195733 hydrocarbon Natural products 0.000 title description 3
- 150000002430 hydrocarbons Chemical class 0.000 title description 3
- 239000004215 Carbon black (E152) Substances 0.000 title description 2
- 238000009835 boiling Methods 0.000 claims description 45
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 24
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000019406 chloropentafluoroethane Nutrition 0.000 claims description 18
- 239000003507 refrigerant Substances 0.000 description 25
- 238000005057 refrigeration Methods 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- MRRMMFGPBHVPDJ-UHFFFAOYSA-N 1-chloro-1,1,2,2,2-pentafluoroethane difluoromethane Chemical compound FCF.ClC(C(F)(F)F)(F)F MRRMMFGPBHVPDJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052731 fluorine Chemical group 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Chemical group 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 239000004340 Chloropentafluoroethane Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical class [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/048—Boiling liquids as heat transfer materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
Definitions
- the invention relates to fluorinated hydrocarbons and more particularly to constant boiling fluorochlorocarbon mixtures which comprise difluoromethane and monochloropentafluoroethane and which are especially adapted for use as high capacity, low temperature refrigeration compositions.
- the refrigeration capacity of a given amount of refrigerant is largely a function of boiling point, the lower boiling refrigerants generally offering the greater capacity at a given evaporator temperature. This factor to a great extent influences the design of refrigeration equipment and aflFects capacity, power requirements, size and cost of the unit.
- Another important factor directly related to boiling point of the refrigerant is minimum cooling temperature obtained in the evaporator during the refrigeration cycle, the lower boiling refrigerants being used to effect the lower refrigeration temperatures. For these reasons a large number of refrigerants of different boiling temperature and capacity are required to permit flexibility in design and the art is presented with the problem of providing new refrigerant-s as the need arises for new capacities and types of installations.
- the lower aliphatic hydrocarbons when substituted by chlorine and fluorine are known to have potential as refrigerants. Many of these chlorofluorohydrocarbons exhibit certain desired properties including low cost, low specific volume, low toxicity and chemical inertness which have resulted in the extensive use of such compounds in a large number of refrigeration applications. Examples of such compounds include difluorodichlorornethane, B.P. 29.8 C., chlorodifluoromethane, B.P. 40.8 C., fluorodichloromethane, B.P. 8.9 C, fluorotrichloromethane, B.P. 23.8 C., and tetrafluorodichloroethane, B.P. 3.5 C.
- a compound having considerable potential as a low temperature refrigerant is difluoromethane, B.P. l.7 C. It has been found that this fluorocarbon posses many of the desired properties for use in refrigeration notwithstanding the presence of two hydrogen atoms which tend to induce flammability which is objectionable in some refrigeration applications. While fluorocarbons of this type are low boiling the limited number of such compounds having the desired refrigerant properties represent widely different boiling points and fail to provide a satisfactory range of low boiling refrigerants of different capacity. Increased activity in the field of eryogenics and low temperature e.g. quick freeze refrigeration gives rise to a need for new low temperature refrigerants representing different capacities than now available.
- An object of the present invention is to provide new low temperatures, low cost compositions especially suitable for use as refrigerants. More particularly, it is an object to provide new refrigerants boiling lower and havmg greater capacity than the low boiling difluoromethane. Another object is to provide new low boiling compositions composed of difluoromethane mixtures which boil at substantially constant temperature and function as a substantially single substance and therefore are useful in producing refrigeration in those systems in which cooling is achieved by evaporation in the vicinity of the body to be cooled. A further object is to provide low boiling difluoromethane compositions which are substantially nonflammable.
- mixtures consisting of difluoromethane and monochloropentafiuoroethane containing approximately 30- 33 mol percent monochloropentafluoroethane form an azeotrope boiling at temperature of about 57 C. Unless otherwise indicated, percentages herein are in terms of mol percent. It has also been found that mixtures consisting of difluoromethane and monochloropentafluoroethane substantially in the range of 13-65% monochloropentafluoroethane have boiling points differing only slightly from the azeotropic composition. Compositions within this range will exhibit only negligible fractionation on boiling and represent useful refrigerants. Further, the mixtures formed by these components result in a reduction in the flammability of difluoromethane such that mixtures containing about 13% or more monochloropentafluoroethane are non-flammable in all proportions in the air.
- difluoromethane-monochloropentafluoroethane compositions with the minus 57 C. plus-minus 0.4 C. boiling temperature represent a marked reduction as compared with the boiling temperature of the lower boiling difluoromethane component.
- the indicated difluoromethane-monochloropentafluoroethane compositions may be employed to provide substantially increased refrigeration capacity over that of difluoromethane and represent new refrigerant compositions useful in obtaining high capacity low temperature refrigeration. Further, flammability of difluoromethane is reduced by admixture with monochloropentafiuoroethane such that all compositions within the indicated range are substantially nonflammable.
- Boiling points of difiuoromethane-monochloropentafluoroethane mixtures were determined using diffuoromethane and monochloropentafluoroethane each better than 99.8 percent pure. All material was dried over P 0 prior to use. The static method was used to measure the boiling points of the mixtures. Weighed amounts of the components were distilled into a bomb and thermostated at constant temperature. To minimize the segregation error, the system was always 50-80% liquid filled. The vapor pressure was measured directly by a Wallace & Tiernan FA- mercury manometer which was accurate to better than 1 part in 1000, and all readings were corrected to normal atmospheric pressure of 760 mm. of Hg at 0 -C., and standard gravity.
- the bath temperature was controlled to better than :0.05 'C., and was measured by an L&N platinum resistance thermometer which was calibrated against an N.B.'S. certified platinum resistance thermometer. The accuracy of the temperature measurements was i0.02 C. Bath temperature was adjusted until the vapor pressure of the mixture was one atmosphere.
- the normal boiling point data are summarized as follows.
- difiuoromethane and monochloropentafluoroethane Apart from use of the indicated amounts of difiuoromethane and monochloropentafluoroethane, make-up of the compositions of the invention requires no special procedures.
- the difiuoromethane and monochloropentafluoroethane employed should be substantially pure, preferably at least about 99.0 percent pure, and contain no substances deleteriously affecting the boiling characteristics of the mixture compositions or use as refrigerants.
- the system formed by herein mixtures of difiuoromethane and monochloropentafiuoroethane provides a broad range of mixture compositions which boil at substantially constant temperature and give a constant boiling composition.
- azeotropic and substantially azeotropic mixtures differ from refrigerant mixtures proposed in the past which offer only a relatively narrow range of useful compositions. While prior mixtures boil generally only about 1-3 C. below the lower boiling component, the mixture system of the present invention results in a relatively large reduction of about 5.0-5.5 C. over the boiling point of difiuoromethane.
- the compositions of the invention may be used in design of refrigeration equipment of reduced size operating at evaporator temperatures of about minus 15 and below to e.g. minus 70-80 C.
- compositions of the present invention exhibit the desired refrigerant properties including low cost, low specific volume, non-toxicity, and chemical inertness, with mixtures containing about 13.0% or more C F Cl being non-flammable in all proportions. In elfect, these compositions combine the valuable refrigerant characteristics of the chlorofluorohydrocarbons with the high capacity, low boiling properties of difiuoromethane.
- the substantially constant boiling properties of mixtures containing 13-65% of C F Cl provide a substantial range of compositions suitable for use in those types of refrigeration in which cooling is effected by condensing and thereafter evaporating the refrigerant in the vicinity of a body to be cooled.
- compositions may be also used in the special situation known in the art to provide additional capacity where needed in equipment designed for difiuoromethane or refrigerants having equivalent capacity. It will be noted that the mixture system disclosed herein may also be used for other purposes including a heat transfer medium, gaseous dielectric, low temperature solvent and power fluid.
- a low boiling composition consisting of a mixture of difiuoromethane and monochloropentafluoroethanc, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 13-65.
- a low boiling composition consisting of a mixture of difiuoromethane and monochloropentafluoroethane, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 15-55.
- a low boiling composition consisting of a mixture of difiuoromethane and monochloropentafiuoroethane, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 25-35.
- the process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafiuoroethane in which mixture the mol percent of monochloropentafiuoroethane is substantially in the range of 25-35, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
- the process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafluoroethane in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 15-55, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
- the process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafluoroethane in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 25-35, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
- Claim 6, line 5, "25-35" should be -l365--.
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Description
Sept. 30, 1969 RD. BROADLEY 3,
FLUORINATEP HYDRQCARBON COMPOSITIONS Filed Oct. 3, 1963 CURVE A BOILING POINT (veo mm. H8 AT 0%.)
' Mon. MouoR LOROPE NTAFLUOROETHAN E T 'INVENTOYR ROBERT D. BROADLEY ATTORNEY United States Patent 3,470,101 FLUORINATED HYDROCARBON COMPOSITIONS Robert D. Broadley, Hanover Township, Morris County, N.J., assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York Continuation-impart of abandoned application Ser. No. 179,237, Mar. 12, 1962. This application Oct. 3, 1963, Ser. No. 313,643
Int. Cl. C09k 3/06; F25
US. Cl. 252-67 -6 Claims This is a continuation-in-part of my application, Ser. No. 179,237, filed Mar. 12, 1962, now abandoned.
The invention relates to fluorinated hydrocarbons and more particularly to constant boiling fluorochlorocarbon mixtures which comprise difluoromethane and monochloropentafluoroethane and which are especially adapted for use as high capacity, low temperature refrigeration compositions.
The refrigeration capacity of a given amount of refrigerant is largely a function of boiling point, the lower boiling refrigerants generally offering the greater capacity at a given evaporator temperature. This factor to a great extent influences the design of refrigeration equipment and aflFects capacity, power requirements, size and cost of the unit. Another important factor directly related to boiling point of the refrigerant is minimum cooling temperature obtained in the evaporator during the refrigeration cycle, the lower boiling refrigerants being used to effect the lower refrigeration temperatures. For these reasons a large number of refrigerants of different boiling temperature and capacity are required to permit flexibility in design and the art is presented with the problem of providing new refrigerant-s as the need arises for new capacities and types of installations.
The lower aliphatic hydrocarbons when substituted by chlorine and fluorine are known to have potential as refrigerants. Many of these chlorofluorohydrocarbons exhibit certain desired properties including low cost, low specific volume, low toxicity and chemical inertness which have resulted in the extensive use of such compounds in a large number of refrigeration applications. Examples of such compounds include difluorodichlorornethane, B.P. 29.8 C., chlorodifluoromethane, B.P. 40.8 C., fluorodichloromethane, B.P. 8.9 C, fluorotrichloromethane, B.P. 23.8 C., and tetrafluorodichloroethane, B.P. 3.5 C. While these chlorine-fluorine derivatives provide an adequate range of refrigerants for many purposes, only a very few boil sufficiently low to offer any potential as low temperature refrigerants. A major reason for this is the presence of the heavier chlorine substituent which generally results in a higher boiling compound than those containing predominantly fluorine or hydrogen.
A compound having considerable potential as a low temperature refrigerant is difluoromethane, B.P. l.7 C. It has been found that this fluorocarbon posses many of the desired properties for use in refrigeration notwithstanding the presence of two hydrogen atoms which tend to induce flammability which is objectionable in some refrigeration applications. While fluorocarbons of this type are low boiling the limited number of such compounds having the desired refrigerant properties represent widely different boiling points and fail to provide a satisfactory range of low boiling refrigerants of different capacity. Increased activity in the field of eryogenics and low temperature e.g. quick freeze refrigeration gives rise to a need for new low temperature refrigerants representing different capacities than now available.
3,470,101 Patented Sept. 30, 1969 An object of the present invention is to provide new low temperatures, low cost compositions especially suitable for use as refrigerants. More particularly, it is an object to provide new refrigerants boiling lower and havmg greater capacity than the low boiling difluoromethane. Another object is to provide new low boiling compositions composed of difluoromethane mixtures which boil at substantially constant temperature and function as a substantially single substance and therefore are useful in producing refrigeration in those systems in which cooling is achieved by evaporation in the vicinity of the body to be cooled. A further object is to provide low boiling difluoromethane compositions which are substantially nonflammable.
In accordance with the invention it has been discovered that mixtures consisting of difluoromethane and monochloropentafiuoroethane containing approximately 30- 33 mol percent monochloropentafluoroethane form an azeotrope boiling at temperature of about 57 C. Unless otherwise indicated, percentages herein are in terms of mol percent. It has also been found that mixtures consisting of difluoromethane and monochloropentafluoroethane substantially in the range of 13-65% monochloropentafluoroethane have boiling points differing only slightly from the azeotropic composition. Compositions within this range will exhibit only negligible fractionation on boiling and represent useful refrigerants. Further, the mixtures formed by these components result in a reduction in the flammability of difluoromethane such that mixtures containing about 13% or more monochloropentafluoroethane are non-flammable in all proportions in the air.
The foregoing difluoromethane-monochloropentafluoroethane compositions with the minus 57 C. plus-minus 0.4 C. boiling temperature represent a marked reduction as compared with the boiling temperature of the lower boiling difluoromethane component. The indicated difluoromethane-monochloropentafluoroethane compositions may be employed to provide substantially increased refrigeration capacity over that of difluoromethane and represent new refrigerant compositions useful in obtaining high capacity low temperature refrigeration. Further, flammability of difluoromethane is reduced by admixture with monochloropentafiuoroethane such that all compositions within the indicated range are substantially nonflammable.
Boiling points of difiuoromethane-monochloropentafluoroethane mixtures were determined using diffuoromethane and monochloropentafluoroethane each better than 99.8 percent pure. All material was dried over P 0 prior to use. The static method was used to measure the boiling points of the mixtures. Weighed amounts of the components were distilled into a bomb and thermostated at constant temperature. To minimize the segregation error, the system was always 50-80% liquid filled. The vapor pressure was measured directly by a Wallace & Tiernan FA- mercury manometer which was accurate to better than 1 part in 1000, and all readings were corrected to normal atmospheric pressure of 760 mm. of Hg at 0 -C., and standard gravity. The bath temperature was controlled to better than :0.05 'C., and was measured by an L&N platinum resistance thermometer which was calibrated against an N.B.'S. certified platinum resistance thermometer. The accuracy of the temperature measurements was i0.02 C. Bath temperature was adjusted until the vapor pressure of the mixture was one atmosphere. The normal boiling point data are summarized as follows.
Normal boiling points of CH F /C F Cl mixture system M01 percent C F Cl Normal boiling An independent check was made on the azeotropic I composition by distillation. Approximately equimolar amounts of CH F and C F Cl were charged into a plate low temperature still. The still had provisions for sampling from the pot and the overhead. About /3 of the initial charge was distilled over at 57 C. This product was placed back in the still and refluxed until equilibrium was established. Samples were then taken from the overhead and the pot and analyzed by vapor phase chromatography. Analysis agreed within experimental error and by calibration of the chromatographs gave an azeotropic composition of 32%i1.0%'. The boiling point of this sample was determined in the above described static equipment, and was 57.26 C.
The data of the above table are represented graphically by the curve A of the attached drawing. The data and drawing show that the difluoromethane-monochloropentafluoroethane mixture system indicated forms a minimum boiling azeotrope within the approximately 30-33 mol percent range of C F Cl. As shown by the drawing, these data establish a curve having a relatively fiat lower contour demonstrating a range of mixture compositions having boiling points which vary only slightly from that of the minimum boiling minus 57.3 C. 30-33% C F Cl compositions. Curve A shows this range to consist of mixture compositions containing about 13-65% inclusive of C F Cl. The l3-65% chloropentafluoroethane compositions indicated each has a boiling temperature variation of less than 0.75 C., from the minimum boiling minus 57.3 C. azeotrope composition. As compositions containing 13-65% C F Cl all boil between about 56.6 C. and 57.3 C., representing a maximum boiling temperature variation within 0.75 C., no significant fractionation occurs on distillation of any compositions within this range, and all such compostions are suited for use as refrigerants.
For most advantageous refrigerant use, it is desirable and preferred to employ mixtures substantially at the 30-33% C F Cl azeotrope compositions if the objective is to avoid even minor differences in liquid and vapor composition. However, since there is no significant boiling point difference in the C F Cl composition range of -35%, for general first class operation these compositions are preferred. In cases where operating requirements are less rigid, compositions in the 15-55% C F Cl range, all boiling about at or below 57 C., are preferred and are eminently suitable since all such compositions boil within substantially 0.25 C.
Apart from use of the indicated amounts of difiuoromethane and monochloropentafluoroethane, make-up of the compositions of the invention requires no special procedures. The difiuoromethane and monochloropentafluoroethane employed should be substantially pure, preferably at least about 99.0 percent pure, and contain no substances deleteriously affecting the boiling characteristics of the mixture compositions or use as refrigerants.
The system formed by herein mixtures of difiuoromethane and monochloropentafiuoroethane provides a broad range of mixture compositions which boil at substantially constant temperature and give a constant boiling composition. These azeotropic and substantially azeotropic mixtures differ from refrigerant mixtures proposed in the past which offer only a relatively narrow range of useful compositions. While prior mixtures boil generally only about 1-3 C. below the lower boiling component, the mixture system of the present invention results in a relatively large reduction of about 5.0-5.5 C. over the boiling point of difiuoromethane. The compositions of the invention may be used in design of refrigeration equipment of reduced size operating at evaporator temperatures of about minus 15 and below to e.g. minus 70-80 C.
The compositions of the present invention exhibit the desired refrigerant properties including low cost, low specific volume, non-toxicity, and chemical inertness, with mixtures containing about 13.0% or more C F Cl being non-flammable in all proportions. In elfect, these compositions combine the valuable refrigerant characteristics of the chlorofluorohydrocarbons with the high capacity, low boiling properties of difiuoromethane. The substantially constant boiling properties of mixtures containing 13-65% of C F Cl provide a substantial range of compositions suitable for use in those types of refrigeration in which cooling is effected by condensing and thereafter evaporating the refrigerant in the vicinity of a body to be cooled. As refrigerants these compositions may be also used in the special situation known in the art to provide additional capacity where needed in equipment designed for difiuoromethane or refrigerants having equivalent capacity. It will be noted that the mixture system disclosed herein may also be used for other purposes including a heat transfer medium, gaseous dielectric, low temperature solvent and power fluid.
I claim:
1. A low boiling composition consisting of a mixture of difiuoromethane and monochloropentafluoroethanc, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 13-65.
2. A low boiling composition consisting of a mixture of difiuoromethane and monochloropentafluoroethane, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 15-55.
3. A low boiling composition consisting of a mixture of difiuoromethane and monochloropentafiuoroethane, in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 25-35.
4. The process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafiuoroethane in which mixture the mol percent of monochloropentafiuoroethane is substantially in the range of 25-35, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
5. The process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafluoroethane in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 15-55, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
6. The process of producing refrigeration which comprises condensing a mixture consisting of difiuoromethane and monochloropentafluoroethane in which mixture the mol percent of monochloropentafluoroethane is substantially in the range of 25-35, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
References Cited UNITED STATES PATENTS 7/ 1934- Midgley et al 25267 6/1953 Iewis 25267 US. Cl. X.R. 62-1l2; 260-659 Po-mso Patent No. 3, 470,101
Inventor(s) m 185! UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated September 30 1069 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 59, "posses" should be -possesses--.
Claim 6, line 5, "25-35" should be -l365--.
(SEAL) Attest:
Edward M. Fletcher, Jr.
Attesting Officer smuzu mu SEALED JAN 204970 WILLIAH E. SGHUYLER, JR. Comissioner of. Patents
Claims (1)
1. A LOW BOILING COMPOSITION CONSISTING OF A MIXTURE OF DIFLUOROMETHANE AND MONOCHLOROPENTAFLUOROETHANE, IN WHICH MIXTURE THE MOL PERCENT OF MONOCHLOROPENTAFLUOROETHANE IS SUBSTANTIALLY IN THE RANGE OF 13-65.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US31364363A | 1963-10-03 | 1963-10-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3470101A true US3470101A (en) | 1969-09-30 |
Family
ID=23216520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US313643A Expired - Lifetime US3470101A (en) | 1963-10-03 | 1963-10-03 | Fluorinated hydrocarbon compositions |
Country Status (5)
Country | Link |
---|---|
US (1) | US3470101A (en) |
BE (1) | BE649080A (en) |
CH (1) | CH460713A (en) |
DE (1) | DE1254587B (en) |
GB (1) | GB1026336A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5232618A (en) * | 1991-09-30 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Substantially constant boiling compositions of difluoromethane and trifluoroethane or perfluoroethane |
US5645754A (en) * | 1993-03-02 | 1997-07-08 | E. I. Du Pont De Nemours And Company | Compositions including a hexafluoroprpoane and dimethyl ether for heat transfer |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1968050A (en) * | 1931-11-19 | 1934-07-31 | Gen Motors Corp | Heat transfer and refrigeration |
US2641580A (en) * | 1951-03-02 | 1953-06-09 | Du Pont | Azeotropic refrigerant composition of 1,1-difluoroethane and monochloropentafluoroethane |
-
1963
- 1963-10-03 US US313643A patent/US3470101A/en not_active Expired - Lifetime
-
1964
- 1964-05-22 GB GB21306/64A patent/GB1026336A/en not_active Expired
- 1964-06-03 DE DEA46204A patent/DE1254587B/en active Pending
- 1964-06-10 BE BE649080D patent/BE649080A/xx unknown
- 1964-08-12 CH CH1053164A patent/CH460713A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1968050A (en) * | 1931-11-19 | 1934-07-31 | Gen Motors Corp | Heat transfer and refrigeration |
US2641580A (en) * | 1951-03-02 | 1953-06-09 | Du Pont | Azeotropic refrigerant composition of 1,1-difluoroethane and monochloropentafluoroethane |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5232618A (en) * | 1991-09-30 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Substantially constant boiling compositions of difluoromethane and trifluoroethane or perfluoroethane |
US5788877A (en) * | 1991-09-30 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Substantially constant boiling compositions of difluoromethane and trifluoroethane |
US5645754A (en) * | 1993-03-02 | 1997-07-08 | E. I. Du Pont De Nemours And Company | Compositions including a hexafluoroprpoane and dimethyl ether for heat transfer |
Also Published As
Publication number | Publication date |
---|---|
CH460713A (en) | 1968-08-15 |
DE1254587B (en) | 1967-11-23 |
GB1026336A (en) | 1966-04-20 |
BE649080A (en) | 1964-10-01 |
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