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802 CHAPTER 50 1965 Guide And Data Book TEMPERATURE , 0E6REES FAHRENHEIT NormaBy itftnd (ramfomr oJL RtdraM froa ftefaesce SI. Fig. 41 .... Solubility of Water in Mineral Oil white paraffin base oil'and a medium-refined naphthene base oil were heated for 30 days at 302 F in sealed tubes containing copper, steel and various refrigerants in addition to.the oil: The refrigerants employed were Refrigerants 12, 13, 22 and 23.' For:a' given oil/ the order-of decreasing plating was 12 >23 >22>13. However, some copper plating waaobserved in all teste, even in the absence of refrigerant. Also, more copper plating occurred with the'medium refined naphthenic oil than with the highly refined paraffinic oil, with the same refrigerant in both inktanceia Other investigators have shown that mineral oils may differ in ability to withstand attack by refrigerants at the elevated Fig;: 42 .... Effect of Air-Pressure on Solubility of Air w.. ! . in Mineral Oil* temperature (e.g., 347 F) of a refrigerant resistance test. Based on an extensive laboratory testing program. Walker, Rosen, and Levy47 have concluded that color darkening, corrosion, wall deposits and copper plating are generally less in paraffin base than in naphthene base oils. Type and severity of refining is also important.40 Refrigerants also differ among themsieves in ability to attack mineral oils. Carbon dioxide and the plain hydrocar bons (ethane, propane, isobutane, etc.) are said to have no significant chemical effect on petroleum oils.* Ammonia' has no chemical effect on well refined, dry oils, but may form soaps and emulsions with poorly refined oils, especially if water happens to be present.**40 The halogensted refrigerants show considerable variation; some (e.g., Refrigerant 14) are practically inert and others (e.g,, Refrigerant 11) react with oils quite readily in sealed tubes at 347 F.4**47 When the test is made with a reactive refrigerant, so far as one can judge visually, the reaction seems to follow much the name pattern with all mineral oils. However, the reaction rate may be slow with one oil and comparatively fast with another. Hence refrigerant resistance is usually evaluated on a time basis. The reaction itself, assuming the oil is tested with one of the more reactive halogenated refrigerants, is almost in variably accompanied by a gradual destructive decomposition of the oil hydrocarbons so that, in time, only a black char, remains (see References 42-45, 47, 49-51). The blackening and charring appears to be associated with the number and kind of atoms in the halogenated refrigerant molecule. It has been observed, in the case of a given mineral oil heated at 347 F with a number of different refrigerants and for time periods up to five years, that the charring reaction occurred only with those halogenated refrigerants which contain more than one chlorine atom in the molecule, e.g.. Refrigerant 11, methylene chloride, Refrigerants 12, 21, 113, etc. Moreover, Refrigerant 11 (CCljF) with three chlorine atoms in the molecule reacted with the oil much more rapidly than Refrigerant 12 (CCUFi) which contains only two chlorine atoms.41 Increasing the number of fluorine atoms at the expense of the chlorine atoms seems to decrease the reactivity; thus an arrangement of com mon and potential refrigerants in order of increasing chemical stability in oil mixtures at 347 F is as follows: Refrigerant 11 <methylene chloride <Refrigerant 21 Refrigerant 12 <methyl chloride <Refrigerant 22 <Refriger ant 13 <Refrigerant 115 <Refrigerant 14. Owing to the widespread use of Refrigerants 12 and 22, the chemical stability of systems containing these refrigerants has been of greatest interest. So far as destructive attack on the oil is concerned, Refrigerant 22 appears less reactive than Refrigerant 12. This difference has been borne out in all com parative studies, some of which were based on the rate of darkening described in the previous paragraph41*47 and others were actual quantitative measurements of the de-' composition products of the reaction.10**1 .; 'Recent evidence obtained by Spauschus and Doderer^ shows that the oil-Refrigerant 12 reaction, catalyzed by iron at 347 F or 400 F, produces substantial quantities of Refriger ant 22 as a primary reaction product. Lagging behind this pri mary decomposition is a complex effect by which acidic de composition products and carbonized sludges are formed. ' Oil-refrigerant reactions are not yet well understood. The lack of understanding stems in large part from the fact that a mineral oil itself is a complex mixture of many different substances. Differences in base types, differences in viscosity grades, differences in refinement, and the catalytic effects of metals, additives, and possible contaminants all are influen tial in altering the reaction possibilities. Other system com ponents (e.g., hermetic motor insulation, etc.) introduce Lubnconfs in Refrigerant Systems farter< complications (see Chapter 60),- and the results of laboratory tests are not always indicative of actual behavior uoder'service conditions. At the present time it is virtually jmppmible and certainly inadvisable to assess the chemical stability of different oil types, or even different oil brands, on ganpjal considerations. After screening by laboratory tests, toe recommended practice for the ultimate selection of a new oil'is ^evaluate the stability on the basis of accelerated life tats inthe system, or in a similar type of system, in which the ml is to be used. REFERENCES - > Oils and Lubricants (Chapter 17, ASRE Data Book, 1949,' 6th ed., p. 299). * L Stride: Kdttemasehinendle (Springei-Verlag, Berlin, Ger many, 1950, d. 81). * K. R. Baldwin and S. G. Daniel (Journal of the Institute of Petroleum, VoL 39, 1953, p. 105). A. Beerbower and D. F. Greene: The behavior of lubricating oils in inert gas atmospheres (ASLE Transactions, VoL 4, No. 1, 1961, P- 87). * Oua and Lubrication (Chapter 13, ASRE Data Book, 1942, 5th ed., p. 185). * Private communication from E. S. Ross, Sun Oil Company. * Unpublished data from Freon Products Division, E. I. duPont deNemoura and Co., Inc. * H. M. Parmelee: Viscosity of refrigerant-oil mixtures at evaporator conditions (ASHRAE Tran&actions, VoL 70, 1964). * H. J. Loffier: (a) Density of oil-refrigerant mixtures. (Kdbetecknik, VoL 11, No. 3, 1959, p. 70). (b) Viscosity of oil- refrigerant mixtures (ibid., Vol. 12, No. 3, I960, p. 71). 10G. Bambach: The behavior of mineral oO-F12 mixtures in refrigerating machines (Abhandhtngen des Devtschen Kaltetech- nischai Verms, No. 9, 1955. (Translated by Carl Demrick.) Also see abridgment in (Kdltetechnik, Vol. 7, No. 7. 1955, p. 187). u V. L. Shipp: Miscibility of Freon (Refrigerant F-12) with mineral lubricating oil (Socony-Vacuum Oil Co., General Laboratories Technical Memorandum, October 23, 1942). " H. J. Lfiffler: Some properties of the binary system R12-R22 and the ternary system R12-R22-naphthenlc mineral oil (Kdltetechnik. VoL 12, No. 9, 1960, p. 256). --- " L. F. Albright and A. S. Mandelbaum: Solubility-and vis cosity characteristics of mixtures of lubricating oils and "Freon- 13 or -115" (Refrigerating Engineering, October 1956, p. 37). M L. F. Albright and J. D. Lawyer: Viscosity-solubility char acteristics of mixtures of Refrigerant 13B1 and lubricating oils (ASHRAE Journal, April 1959, p. 67). UJ. L. Little: Viscosity of lubricating oiI-Freon-22 mixtures (Retoiqerating Engineering, November 1952, p. 1191). " Private communication from A. B. Culbertson, Shell Ofl Company. 17 0. M. Bosworth: Predicting the behavior of ofls in refrigera tion systems (Refrigerating Engineering, June 1952, p. 617). " H. O. Spauschus: Thermodynamic properties of refrigerant- oil solutions (ASHRAE Journal, April 1963, p. 47; October 1963, P- 63). . l* W. O. Walker. A. A. Sakhanovaky, and S. Rosen: Behavior of refrigerant oOs and Genetron-141 (Refrigerating Engineering, March 1957, p. 38). ** H. J. Lomer: The effect of the physical properties of mineral oils on their miscibility with the refrigerant Frigen 22 (CHFfCI), Abhandhtngen des Deutschen Kdltetechnischen Veretns, No. 12 (C. F, Mailer Verlag, Karlsruhe, Germany, September 1956). a H. J. Loffier: The miscibility of synthetic oils Fluisit S55K and Polyran M-15 with Frigen 22, Frigen 13 or mixtures of Frigen 22 and Frigen 13 (Kdlteteehnik, VoL 9, No. 5, 1957, p. ** Cloud and Pour Points. (Chapter 4, Physical Properties of Lubricants, The American Society of Lubrication Engineers. 1951, 2nd ed., p. 47). C. R. Begeman and V. A. Williamitis: Refrigeration Appa ratus (U. S. Patent 3,092,981, June 11, 1963). ** W. O. Walker and W. R, Rinelli: The separation of wax from oil-refrigerant mixtures (Refrigerating Engineering, June 1941j*. 395). * H. J. Loffier: Separation of Frigen-insolubles (paraffin) from mineral oil-Frigen 22 mixtures (Kdltetechnik, Vol. 9, No. 4, 1957, P- 103). Privatecommunication from A. W. Jenkins, Humble Oil A Refining Co. 803 07 A. F. Brewer: Good compressor performance demands the right lubricating oil (Refrigerating Engineering, October 1951, p.965). v- 11 Private communication from B. Y. Carty, Texas Company. ** J. D. Bopp: Determination of moisture in refrigeration oils (Refrigerating Engineering, September 1951, p. 891). See also: F. M. Roberts and H. Levin (Analytical Chemistry, VoL 21, No. 12, 1949, p. 1553); R. H. Prince (The Analyst, VoL 78, October 1953, p. 607); R. Weber (Kailetechnik, VoL 6, No. 10, 1954, p. 267); H. Mandel (ibid., VoL 6, No. 10, 1954, p. 269); Bulletin B-23 ("Kinetic" Chemicals Division, E. I. duPont deNemoura and Co. Inc., 1956; J. D. Morton and L. K. Fuchs, Determination of moisture in fluorocarbons (ASHRAE Journal, May 1960, p. 62); H. G. Moale and W. Wolf (Kdllelechnik, VoL 13, No. 9, 1961, p. 304). M R. T. Divers: Better standards are heeded for refrigeration lubricants (Refrigerating Engineering, October 1958, p. 40). a F. M. Clark: Water solution in high-voltage dielectric Liquids (Electrical Engineering Transactions, VoL 59, No. 8, 1940, p. 433). E. T. Neubauer: Compressor crankcase heaters reduce oil foaming (Refrigerating Engineeering, June 1958, p. 52). " P. Berliner: (a) Heating of crankcase housing in Frigen com pressors. (Kdltetechnik, Vol. 11, No. 9, 1959, p. 289); (b) G. Stig: Reduction of the oil concentration in the circulating refrigerant (ibid., Vol. 13, No. 9, 1961, p. 302). ** A. Thelen: Lubrication of bearingB by means of oil-refrigerant mixtures. (Kdltetechnik, Vol. II, No. 10, 1959, p. 341). * R. W. Thorpe and R. G. lanes (Industrial and Engineering Chemistry, Vol. 41, No. 5, 1949, p. 938). * S. F. Murray, R. L. Johnson, and M. A. Swikert: Difluoro- dichloromethane as a boundary lubricant for steel and other metals {Mechanical Engineering, Vol. 78, No. 3, 1956,'p. 233). 07 G. R. Fox and R. C. EHwell: Radioactive determination of bearing wear in refrigerator compressors (Lubrication Engineer ing, Vol. 15, No. 4, 1959, p. 144). " C. C. Gambill: Application of radioisotope wear study tech niques (General Motors Engineering Journal, VoL 5, No. 2, 1958, p. 21). " E. W. McGovern: Copper plating in refrigerant compressors (Refrigerating Engineering, July 1939, p. 31). 40 C. J. Rizxuti, G. D. Staffin, and A. W. Jenkins: Effects of ad ditives and oil refining on refrigerant-refrigerator oil stability (ASHRAE Journal, July 1962, p. 31). 41 U. S. Patents: F. L. Koethen, 2,186,028, Jan. 9, 1940; Downing and Markwood, 2,212,826, Aug. 27, 1940; Cook and Bishop, 2,523,863, Sept 26, 1950; Bishop and Cook, 2,552,084, May 8, 1951; Davidson and Seits, 2,824,061, Feb. 18, 1958. H. M. Elsey, L. C. Flowers, and J. B. Kelley: A method of evaluating refrigerator oils (Refrigerating Engineering, July 1952, p. 737). A. H. Shaw and A. O'B. Brandon (Proceedings of (he Insti tute ofRefrigeration, Vol. 44, 1947-48, p. 93). 44 H. Steinlc: (a) Sulfur dioxide resistance and resin content of refrigerator oils (Kailetechnik, VoL 1, No. 1, 1949, p. 14). (b) Chemical reactions between refrigerants and oils in refrigerators (ibid., Vol. 2, No. 7, 1950, p. 174). (c) Hie temperature resistance of nonmetallic materials in refrigerators (Werkstoffe vnd Kor- rosion, VoL 3, No. 11, p. 419). (d) Determination of refrigerant resistance of refrigerator oils (Kdltetechnik, Vol. 6, No. 12, 1954, p. 342). (e) Experiments on copper plating in refrigerators (ibid., Vol. 7, No. 4, 1955, p. 101). See also Reference 2, p. 46 and pp. 108-109. 41 H. Steiole and W. Sceman: (1) Copper plating in refriger ating machines (Kdltetechnik, VoL 3, No. 8, 1951, p. 194). (b) Cause of copper plating in refrigerators (ibid., VoL 5, No. 4, 1953, p. 90). * H. O. Spauschus: Copper transfer in refrigerant-oil solutions (ASHRAE Journal, June 1963, p. 89). 47 W. O. Walker, S. Rosen, and S. L. Levy: (a) A study of the factors influencing the stability of the mixtures of Refrigerant 22 and refrigerating oils (ASHRAE Transactions, Vol. 66, 1960, p. 445); (b) Stability of mixtures of refrigerants and refrigerating oils (ASHRAE Journal, June 1962, p. 66). 40 F. Musgrave (Refrigeration and Air Conditioning News, Vol. 6, No. 9, 1939, p. 19). 4t EL Steinle: Testing refrigeration oils (Refrigerating Engineering, October 1953, p. 1065). 40 D. E. Kvalnes and H. M. Parmelee: Behavior of refrigerants 12 and 22 in sealed tubes (Refrigerating Engineering, No vember 1957, p. 40). u H. O. Spauschus and G. C. Doderer: Reaction of Refrigerant 12 with petroleum oils (ASHRAE Journal. February 1661, p. 65).