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ft** JE> BetterTKingt-for Better Livin frfr f--^-ttrrouyti Chmistry technical report DP-5 "FREON" 21 FLUOROCARBON E. I. DU PONT DE NEMOURS & COMPANY (INC.) "FREON" PRODUCTS DIVISION WILMINGTON, DELAWARE 19898 u s. Better things for better living.. .through chemistry r*. co * eg rH tH 9 Copyright 1966 by E. 1. du Pont de Nemours and Company, Wilmington, Delaware 19898 "FREON" 21 FLUOROCARBON _r.t roou i or. "Freon" 21, dichloromonofiucrometha.ne, has properties which make it suitable for use as a refrigerant, brine, aerosol propellant, and solvent. The physical properties of "Freon" 21 are summarized in Table I. Density The liquid density may be expressed by dx = 91.518 - 0.077121 - O.ODOOoOlt2 where dj = density of liquid in Ib/cuft t = temperature in ? The average deviation from experimental data by this equation is less than 0.05? over the temperature range -20? to + lcQF. liquid densities at various temperatures are given in Table II. The vapor density at various temperatures is given in Table III. Equation of State The equation of state in the Beattie-Bridgeman form is: P = (0.0003593T - 0.2038) d3 + (0.004642T - 7-316) d2 + 0.10427Td where p = pressure in Ib/sq in absolute T = temperature in R = F + -459.6 d = density of vapor in lb/euft The equation gives less than 0.4% average deviation from experimental data over the pressure range of 4 to 310 psia. EID11288 Solubility In Water "Freer." 21 solubility in water fits the Valer.tiner equation: log Y. = A + B/T + C log T where where K = g/1 (psi a), T = K K = lb/ gal (psia), T = 0R A = -50. 222 A = -5t .272 3 = 3529 . 025 3 = 635 2.24 5 O = 15.5 56 C = 15. 556 rp abl e IV giv es the solubility of "Fr eon" 21 in water at var ious t emp erat ures Solubi lit v of Wat er Table V gives the solubility of water in "Freon" 21 at various temperatures. Specific Heat The specific heat cf the vapor at constant pressure is ex pressed by : C- (1 atm) = 0.1264 + 0.000134t whe: C3 = specific heat of the vapor at constant pressure in Btu per lb oer O -- = temoerature in F This equation gives an average deviation from experimental values of less tna.n 0.1* over the temperature range of 100 to 275F. The specific heat of the vapor at constant volume is expressed by: Cv = 0.1070 + 0. 000l40t Table VI reports Cp and Cv at various temperatures. The specific heat of the liquid is given in Table VII. Surface Tension Table VIII gives the value of the surface tension of "Freon" 21 at various temperatures. EID11289 2 Tnermal Conductivity Thermal conductivity tares is given in Table 1 i,:ie .s r.: various temoeralonductivgtv =.U /. . V- do'" ^ssurs ine vapor pressure c-r' . --Ireon" 21 is giver, by: p0rr. p = ^2.7-03 _ 2 -3 13.0295 log- 0. 0C-39551T v-ner e ? = pressure in Ib/sq in absolute 7 = temperature in 0 ?: = F + 453-5 This equation gives an average deviation from experimental data of 0.4 over the pressure range cf 2.5 to 400 Table XI rivesS the vapor pressure cf "rreor." 21 at various temperatures. Viscosity The change in viscosity with temperature of liquid "Freon1 is shown in Table XII and for ''Freon" 21 vaoor in Table XIII. S clubilit v 'Freon" 21 is the sol ve r. t >on" fluorocarbon series. The presence cf one hydrogen and two chlorine atoms in th; molecule is apparently an arrangement that imparts good solvent properties to t he mol number almost as high c. S tha' "IS u T V 6 * 0 r'' "r'> ^ 0.0 s.n r.eariy twice a: great as that c "Pre 1 ii. The solubility relationships of "Freon" 21 with cL vvaarriety of other solvents are given in Table XIV and the solubility of various organic acids in "Freon" 21 is given in Table XV. The solubility of water in "Freon" 21 and of "r'recn" 21 in water is given in Tables IV and V. COMPATIBILITY WITH MATERIALS Elastomers "Freon" 21 has more effect on elastomers than other "Freon" fluorocarbons. Table XVI gives percent linear swelling data for some typical elastomers. Metals Tests at 130F for 60 days in the presence of free water with "Freon" 21 give a penetration rate on 1020 CR steel of 127 x 10-6 EID11290 3 inches per month and with A.1 2S a rate of 357 x 10-6 inches per month. A copper and steel combination was run at 250F for 60 days with dry "Freon" 21 and the penetration rates were found to be 5 x 10" inches per month for copper and 8.5 x 10-6 inches for 0 2 0 2 R 5 Z- 0 s 1 itt^e or no e::ect on ny_on, 3 i y r z n y 2 6 n ~ r* ^- scene ch1cr~ de 5 and phenol :-rmaIdeny ae serious attacks some other typ 3 ~ -P Oi -- u 1 a St ics . The eon" ii on several plastics is s hown in m ao 1 e XVII. _nese resu > G. "e on measurements of h e li.n G p r* swell ing of tes: o: es suom manv noai*r' i cations in the licuid chase f ;r se ve ra days. g n G ais ar CL vaiia bi o it is re ccro mended that ;ests snou. oe maae > u- ic to b o used under specific use conditions. 'pvrr.i'/ T Tt :ted by 1A day, room' 0 om te mp er ature , imme r^ sio.n in liquid "Freon" 21 while rormvar and "Lecton" insulating materials were softened to some degree. 3T A5T LITY The stability 'Freon" 21 to hydrolysis in the presence of water is good under neutral or acidic conditions. Under alkaline conditions it will hydrolyze quite rapidly and should not be used when the pH is higher than 7. Measured hydrolysis rates have been found to be less than 0.01 grams of "Freon" 21 per liter of water per year at 1 atm pressure and S5F with water alone. This rate increases to 5-2 grams per liter per year in the presence of steel. In the presence of steel at saturation pressure and 122? the rate increases to 5 grams of "Freon" 21 hydrolyzed per liter of water i'6r v 6 c,r*. c/ . i C. k n-- ;aied tube tests with copper, iron, aluminum, and oil showed ;1 stored at 2pOF for 56 cays was as stable as 11 stored at l60F for 55 days. HYDRATE FORMAT I ON it.xo d ny: :ontaininz 17 moles of water and navir.g a meeting point 8.51 + 0.0J The heat of formation has been calculated as ;3 Kcal/gm mole. BRINE APPLICATIONS In spite of its low boiling point of A8F, "Freon" 21 can be used as an intermediate-range brine as it has a freezing point of -211?. FLAMMABILITY Quoting from Underwriters' Laboratories' Report MH-2630, "The Comparative Life, Fire and Explosion Hazards of Dichloromonofluorome t h an e " : EID11291 "No propogation of flame was observed in limits of flammability tests with dichloromonofluoromethane in specially designed apparatus even when the initial temp erature of the vapor-air mixtures was raised to 212F. "The ignition temperature of dichloromonofluoro methane was found to be 1025.6F. "Dichloromonofluoromethane is practically nonflammable and nonexplosive at ordinary temperatures, but at higher temperatures under favorable laboratory test conditions is capable of forming weakly combustible mixtures with air. "Formation of combustible mixtures by dichloromonofluoro methane, however, under practical conditions even at higher temperatures is extremely unlikely, and its fire hazard, therefore, is very small." TOXICITY Comparisons of the relative toxicity of a number of compounds have been made by the Underwriters' Laboratories and divided into groups according to their toxicity. "Freon" 21 has been rated as much less toxic than Group ^ but somewhat more toxic than Group 5. "Freon" 113 is also in this category. For comparison, methylene chloride is rated as somewhat more toxic than "Freon" 21, while "Freon" 21 is rated somewhat more toxic than "Freon" 11 and carbon dioxide. A Threshold Limit Value has been established for a number of chemical products by the American Conference of Governmental Indus trial Hygienists. These values represent conditions of concentration at which it is believed that nearly all workers may be repeatedly exposed day after day without adverse effect. They are based on the best available information from industrial experience, from experi mental studies and when possible from a combination of the two. A value of 1,000 ppm by volume is the highest rating given any product except carbon dioxide. "Freon" 21 has been given a rating of 1,000 ppm by volume as has "Freon" 11 and "Freon" 12. Although "Freon" 21 is low in toxicity, the possibility of injury (or death) exists in unusual situations or if it is deliberately mis used. Good ventilation should be provided in areas where high concen trations of vapors might accumulate. Additional comments on the "Freon" compounds and safety are available in "Freon" Products Bulle tin S-16. 5 EID11292 Table I. PHYSICAL PROPERTIES OF "FREON" 21 FLUOROCARBON r crir.uiE Molecular Weight Boiling Point, C 0F Critical Density, g/cc 1b/cuft Critical Pressure, atm psia Critical Temperature, C 0F Critical Volume, cc/mcl cuft/lb Density Liquid, 11?, g/cc lb/cuf t Vaoor, S b .d., g/1 lb/cuft Dielectric Constant Liquid, 28C Vapor, 30C, 0.5 atm Dipole Moment, Debyes Freezing Point, C F Heat of Vaporization at b.p. cal/g Btu/lb Kauri-Butanol Number Refractive Index, 77F Relative Dielectric Strength, N=1 Solubility in Water, 11?, wt.? -n ,, _ 2 r 102.93 8.92 US. 05 0.522 32.5 51.0 750 178.5 353.3 197 0.0307 1.366 85.28 4.57 0.285 5.34 1.0 C 3 5 1.29 -135.0 -211.0 57.86 104.15 102 1.354 1.85 0.95 EID11293 Table I. (Cont'd) Solubility cf 'water, 11?, wt. S oDj.ucili'ty r's.r.rr: Specific Heat liquid, 77?, cal/'g)(C) Vanor, 1 atm, 77?, cal/()(C) Specific Heat Ratio Surface Tension, 11?, dynes/cm Thermal Conductivity, 11?, 5tu/(hr)(ft)(0F) Liquid Vapor, 1 atm Vapor Pressure, psia, 70F 130F Viscosity, 77?, cer.tipoise Liquid Vapor, 1 atm 0.13 B. 0 0.256 o.uo 1.175 20 0.063 0.00569 23.1 6p.2 0.3^ 0.011 Table II. LI QUIT TENSITY 0? "FREON" 21 AT VARIOUS TEMPERATURES e m.t. -A0 -2 0 0 20 A0 60 80 100 12 0 -A0.0 -23.9 -17.8 - b. 7 A .A 15.6 26.7 37.8 A 8.9 t/CC 1.51A 1. A 9 0 1. A6 1. AAl 1. A 15 1.389 1.362 1.335 1.306 Lr.Nbj.TY Lb/cufa 9b- 52 of. 0A 91.52 69.96 68.35 86.71 85.03 83.31 81.5A lo/mal 12.6A 12. AA 12.23 12.03 11.81 11.59 11.37 11.1A 10.90 EID11294 o 7 Table III. VAPOR DENSITY OF "FREON" 21 AT VARIOUS TEMPERATURES Temp. 0 77 U n -IQ -2 0 0 23 10 60 80 100 120 ^ 9 -17.8 - t. 7 1.1 -5.6 26.7 37.8 18.9 O O -4 1 DENS I T Y p/1 ib/cuft 0.5 0. 9 1.5 2.5 3.9 5. 3 3.3 11.7 16.0 0.03116 0 0^0 L i 0.09662 0.1565 C.2121 0.3606 0.5201 0.7292 0.9936 Table IV. SOLUBILITY OF "FREON" 21 IN WATER AT VARIOUS TEH? Terns. vn 62.1 67.8 125.6 167.0 2 3.0 31.0 52.0 75.0 SOLU BILIT Y g/iiter 1 o / g a 1. W at e r 17.7 16.9 16.0 lo.O 0.118 0. Ill 0.131 0.131 ; ;^ r: is ur /o 1.77 1.69 1.60 1.60 b-l c. V SOLUBILITY OF WATER IN LIQUID ''FREON" 21 AT VARIOUS TEMP. O -p emp. 100 37.8 90 32.2 - 60 2 d . 7 70 21.1 6 0 15.6 50 13.0 10 1.1 30 - 1.1 20 - 6.7 13 -12.2 0 - 10 - 20 - 30 - 10 -17.8 -23.3 -28.9 -31.1 -10.0 - 50 - 60 - 70 - 80 - 90 -100 -15.6 -51.1 -56.7 -62.2 -67.8 -73.3 Solubility, Wt. 0.1980 0.1700 0.1110 0.1150 0.0$60 0.0800 0.0615 0.0512 0.0393 0.0311 0.0260 0.0205 0.0158 0.0118 0.00Q0 0.0066 0.0019 0.0035 0.0025 0.0017 0.0012 EID11295 8 :ao A? j ? ' - aJ^ o 0-- -4 3 -20 0 20 40 rnp. 0 r1 -4 0.0 -23.9 -1 ( , 5 -6.7 4.4 60 ' 80 100 12 0 14 0 160 2. Z- 0 26.7 37.3 43.9 50.0 71.1 Specific Heat 3tu/(lb)(?) 0.234 0.236 0.238 0.241 0.2 45 0.2 4 q 0.25 4 0.2 50 0.267 0.2 7 5 0.265 ON" Ti ^ mp. UF "C -40 0 40 80 120 -40.0 -17.8 4.4 26.7 4b.9 Surface pension dyne s/cm 27.8` 24.4 21.0 17.8 14.7 ^^771 ^ rpT]p~ n 9 EID11296 r rr. a IX. jRMAL CON "FREON" d i ? rnij. --- 57?-- c -4o -4 0.0 -20 -28.9 0 -17.8 20 - 6.7 4 0 4.4 Tnermai Concuctivity 3tu/(hr)(ft)(0 F) 0.0817 0.0785 0.0752 0.0720 0.0688 ' 60 15.5 80 26.7 100 37.3 12 0 43.9 mo 60.0 lbO 71.1 O.0656 0.0623 0.0591 0.0559 0.0527 0.0495 Table X. THERT-1AL CONDUCTIVITY OF "FREON" 21 VAPOR AT VARIOUS TEMP. Temp. F 50 10.0 100 37.8 150 65.6 200 q; t u 250 121.1 300 148.9 Tnermai Conductivity 3tu/(hr)(ft)(F) 0.0055 0.0058 0.0060 0.0063 ' 0.0066 0.0069 Table XI. yap: PRESSURE 'FREON" 21 VARIOUS TEMPERATURES smp. F 0 c -40 -4 0.0 -20 -23.9 0 -17.3 20 - 6.7 40 4.4 Vapor Pressure psia mm rl 1.358 2.578 4.582 7.699 12.32 70.2 133.3 237.0 393.2 637.1 60 15.6 18.90 80 26.7 27.96 100 37.8 40.04 120 48.9 55.75 140 60.0 75.72 160 71.1 100.6 977.4 1446.0 2070.7 2883.1 3915.9 5202.5 EID11297 10 'able XII. VISCOSITY "FREON" 21 LI :d at varidi TEMPERA T U RE S Dole XI vi: J '-JIV V PIOUS r^r T-.O p A nrn " TTT Z* - Tr mr . cF 0r 50 10.0 100 37.0 150 65.5 2 00 93.3 2 5 0 121.1 30 0 125.9 Viseosity 0.0103 0.0119 0.0130 0.01^0 -R -1 -- 0 0.0150 -v Q- "FREON " IN VAR PC;C " A ' * 12.22 ?SIA Solvent Acetic acid Acetyl acetone Aniline A.nis ole oenzalaehyde Cellosolve acetate Cyclone xylamine De c a 1 in 3,3-Dichloro-n-propyl ether L'ietnyl ether of diethylene glycol Diethyl phthalate Diethylene glycol Dimethyl aniline r Ti - - A IC'C* V solve".: Sc-vent - "p^eon11 21/ 100 f solvent 65.0 --1 nW/ o*. n 35.5 67.3 75.0 102.0 107.0 27.2 23.8 113.0 56.1 23.5 69.5- Dimethyl ether of 12 0.0 diethylene slyco1 Dimethyl ether of 111. 0 tetraethyiene Five 0. OXcJZl 107.7 Ethvl ether of di- 102.0 ethylene glycol ac state Ethylene glycol 10.0 Formamide Heptaldehyde ' 7.5 97.9 Nitrobenzene 27.1 Phenol 26.9 Tetralin Triethyl ohosohate ^7 5 113.2 Triethylene glycol 35.8 Trimethylene elycol 10.6 11 Table XV. SOLUBILITY OF VARIOUS ORGANIC ACIDS IN "FREON" 21 AT ROOM TEMPERATURE __________________ elastomer Solubility At . % Elastomer Solubility Wt. I Adioic p-Aminoben zoic An t Tl I* aSi L11 c Azelaic Benzoic c ,m,D-Cr.iorobenzcic p-Hydrcxybenz oic Isophthalic Laurie Myriseic 1-Naohtnoic 2-Napnt hylac ry1ic o,m,p-Nitrobenzoic o --1 1 1 LT\ O <0.1 <3.5 <1.3 <0.1 <1.0 <0.5 <0.5 <1.0 <30.0 <20.0 <0.5 <0.5 Oleic Palmitic Pelargonic Phthalic Pvromellitic Salicylic Stearic Suberic Terephthalic o-Toluic m-Toluic p-Toluic Trimellitic <50.0 <10.0 <50.0 <1.0 <0.5 0.5 - 1.0 <10.0 <0.1 <1.0 0.5 - 1.0 10.0 -20.0 <0.5 <0.5 Table XVI. TEMPORARY LINEAR SWELL OF VARIOUS ELASTOMERS IN "FREON" 21 _______________________ "Adiorene" C, urethane "Aaiprene" L, urethane "Compar" 1001, polyvinyl alcohol "Compar" 1002, polyvinyl alcohol "Compar" 1003, polyvinyl alcohol Neoprene W "Nordel", hydrocarbon "Silastic" 50, silicone Percent Linear Swell 7 aavs a R.T. 7 ciavs -a 1S0F 54 41 8.3 6. i) 3.7 22 23 S9 78 41 5.7 6.0 5.3 25 25 51 Table XVII. LINEAR SWELLING OF PLASTICS IN LIQU: D "FREON" 21 AT ROOM TEMPERATURE elastic % Linear Swell Cellulose acetate Cellulose nitrate Methyl methacrylate Nylon Phenol formaldehyde Polyethylene Polystyrene Polyvinyl chloride Polyvinylidene chloride "Teflon" TFE resin disintegrated disintegrate d disintegrated 0 0 4.5 disintegrated 15 1 0 EID11299 12 FOR FURTHER INFORMATION Please contact one of the following offices: 701 Welch Road Wilmington. Delaware 19898 Palo Alto, California 94304 or Phone: 774-7373 Phone: 326-2840 (Area Code 302) (Area Code 415; r The information contained herein is based on technical data and tests which we believe to be reliable and is intended for use by persons having technical skill, at their own discretion and risk. Since conditions of use are outside of Du Font's control, we can assume no liability for results obtained or damages incurred through the application of the data presented. Publication of the information in this bulletin should not be understood as permission or recommendation for the use of ''Freon'' compounds in violation of any patents. E. I. DU PONT DE NEMOURS & COMPANY INCORPORATED "FREON" PRODUCTS DIVISION Wilmington, Delaware 19898 WORD U v ; M O" Better Things for Better Living... through Chemistry printed n i. S. E1D11300