Chinese J. of Chem. Eng. » 6(2) 174182 (1998) RESEARCH NOTES Determination of Thermodynamic Parameters of Some Fluorochlorohydrocarbons in Acetone by Gas Chromatography at Low Temperature and Pressurization Wang Lihua( i) Department of Chemical Engineering, Zhejiang University, Hangehou 310027, China Keywords low temperature, pressurization, chromatography, fluorachlorohydracarbons, thermodynamic parameters 1 INTRODUCTION Gas chromatography (GC) has been proved to perform satisfactorily in vapor-liquid equilib rium measurements and in the study of solution theory. Infinite dilution data are useful not only for design calculations but also for theoretical development of correlations. Studies in this field have been carried on at the Zhejiang University!*~*). As is well known ,common GC is only applicable to the stationary liquid of higher boil- ing point in its stationary state". A gas chromatograph to perform under low temperature and under pressurization conditions has been developed by the author. Fig.1 gives a schematic flow diagram of the experimental device. With this device, activity coefficient 72, relative volatility af,, partition coefficient K, equilibrium ratio &, Henry’s coefficient H and selectivity S!, at infinite dilution for CHCIF;,CCI,F;.C;F,,C,F, in acetone at temperature —16—-0C and pressure 294—1471kPa were determined. The data obtained were then processed by computer and satisfactory results were achieved 2. REAGENTS, APPARATUS, PROCEDURE AND EXPERIMENTAL DATA Bearer Chromosorb GAW-DMCS,Mesh size 80 Stationary liquid (Extractant); Acetone (AR) Samples :Chlorodifluoromethane (CHCIF;),(F22), T: Dichlorodifluoromethane (CClF:),(F12), Ty= Perfluoropropene (C;F,)+ Ty=—29.0C, purity + 99% (wt) Octofluorocyclobutane(C,F,), Ty =—6.06C, purity = Since during the experimentation process, carrier gas was flowing in continuum losses purity + 999% (wt) 29.8'C, purity + 99% (wt) in stationary liquid are unavoidable. Therefore, a presaturator containing acetone was being installed in front of the column tube, in order to reduce the loss microacetone of loss can be retrieved through the condensate pipe. The column was 6 X 1. 5 X s in stationary liquid. The Received 1997—-07—11, sccepted 1997—12—15.ony Th madynoinie Pararsete of Sam, Fluvrocstorahy@recurinms 175 le Now divgcum for GC performing under tow temperature and pressurization conditions 1 high pressace enricr gas eslindsry < presiues reducers © deasionars 4 —high pressure needle valves stshilins Pe sawe va €4 8 —prveision presmue goges / poesmuretory 8 high-pressure six-way valves 1 raeamaitatiee pipes jratihc clammy 11 shormal eomductivity cell detectory 12-~condeneste pes 14 rotameters [1 soap film Finemicters 15 thermal comhictiity cell deteetor support and regulatory 1S eecorders 17 vacuum pamp) 18--balloon tyre: 19--high pressure cut-off valver 20~precision thermometer securate to 0-14 21 low temperature shermutaty 22—cold traps 23--coiling chiller Sodmm in dimension. The pressure of the GC column was controlled by the high-pressure needle valve. The carrier gas flow rate at the column outlet (at room temperature ) was determined by soap film flowmeter. The samples were injected through the high-pressure six way valve The volume of the quantivative pipe was L ml The hearer was dried for 4h at 2000. The GE column wah dry bearer was then installed into a commercial GC. The Vaporizer temperature was controlled at 70. ,and the carrier gas How rate was controlled at Jom! min! The column teny erature was controlled at room temperature. An analytical Faluice wos used for weighing thy GC eclunin with dry bearer and wer bearer respectively. Fresh columns were prepared for cach isotherm Experimental data are give in Tables 15, Table J Experimental data ut column temperature 0 be % KP reb-min TRE ~ oe 972-4 mas 0.9965 368. 578 98.2 ore 449 153.5 0.86 3.80 v9.8 40. 0.88 pitas _ ee ett Wee We 58z0@ Way 0. 42608 Chinese J. ChE. 662) 174 (4998)176 Chinese J. Ch. E. (Vol. 6. No. 2) ‘Table 2 Experimental data st column temperature — 4(C Adjusted retention time ¢, min % a b fe iu c kPa kPa l-min“? cr Fiz Fee 28.0 304.2 296.0 27.60 0.83 25.0 305.2 297.0 27.50 185, 25.8 09.8 201.0 76.80 raat 25.9 586.7 378.2 53.10 0.78 168 25.9 580.6 $80.8 53.33 10.05 25.8 989.7 979.5 86.96 0.65 25.9 986.8 94.6 86.33 8.83 23.7 met.9 nme 108, 40 0.82 25.6 1180.9 1170.6 108.50 B.5 1180.0 116.5 108.40 651 25.2 ware. 1462.0 127.30 0.43 25.1 uae. 1468.8 127.50 0.96 25.3, 1475.1 1464.4 128. 30 613 P= 101. 231KPe Wie=0. 45968 Wis=0- 20838 Table 3 Experimental dats at column temperature —8'C Tr a m fe c Li oe alemin- CaF Fig Foe CFs 24.70 298.2 286.2 m8 0.79 24.85 297.2 283.2 27.09 1.69 24.90 299.2 289.2 27.40 10.90 24.60 305.0 295.2 28.91 0.66 25.40 son 581.6 54.05 0.88 25.40 593.4 583.6 54.55, 17 25.20 597.3 587.2 58.05 nas 24.70 54.2 saa st.33 068 25.30 983.7 on.9 90. 36 0.78 25.20 981.7 970.0 21.60 1.63 25.70 984.7 92.7 92.90 10.83 24.90 990.7 94.7 88.37 ost 26.15 1179.8 1169.8 108. 98 0.75 1.60 26.30 n77.9 1168.0 110.09 10.04 25.10 1189.6 1169.8 103.45 0.53 26.10 1479.9 1469.9 136. 36 on 26.10 1478.0 1464.0 137.77 1s 28.10 17.0 1465.1 136. 99 9.85, 25.30 1480.9 14583 132.60 oar P=100.125KPa Wis 0-3684¢ Wis=0.3509¢ * p= 102-045kPa Wis 9. 3833g Wir = 0. 3636g June, 1998Determination of Thermodynamic Parameters of Some Fluerochlorohydrocarbons: 17 ‘Table 4 Experimental data at column temperature — 12 tr hn b he ‘Adjusted retention time f+ in| c kPa kPa salma cr ra Ye 25.10 50.9 283.3 2.15 2.00 25.30 305.8 284.3 2.31 an 25.70 3049 rae 26.43 2.63 4.30 603.0 si.6 54.05 1.99 25.18 599.0 515.6 34.55 4.06 24.10 ong 519.6 34.95 26.49 23.40 996.2 965.1 88.89 vse 23.80 998.2 968.8 ar.59 3.80 2.60 mee ose e0.e0 pos 23.15 ez. 1160.3 108.12 1.68 ast v.90 er 1160. 109.29 an mao 89.5 158.2 133.78 1.60 40 488.5 156.4 133.78 aa v.40 1487-5 1454.5 134.08, 22.08 p=100.871KPe Wis 0.6999q Wis 0.6547 le § Experimental date at column temperature —16 he > » he ‘Adhsed retention time f+ min kPe kPa wi-min~! CFs Fiz Fez na 299.7 298.7 ” 0-8 2.2 298.8 2ar.s a 187 1 18 286.6 1 1.08 20.1 590.0 seo 54.55 0.90 2 sao se 4.55 noe 20.1 504.9 sto sso ian 2 986.2 975.2 21.05 oe? 20.3 985.2 ome 20.96 Le 107 at 1184.3, 1173.3 108. 09 on Ls 1.3 2.5 u7e.s 1460.3 11.87 on ns 1480.5 wre 133.33 149 a4 82.4 urs 135.14 10.50 P=100-665KPe Wiy= 0.3642" Wis—0-3057K 3° CALCULATION FORMULAE (Q) Mean pressure in column? POAC) ees w 3 Capa? Chinese J. Ch, B. 6(2) 174 (1998)178 Chinese J. Ch. E. (Vol. 6. Ne. 2 (2) Mean carrier gas flow rate in column!!!” TP Dep @ - Compressibility factor of the mixed species is calculated by the following formu Za VABg/V g= PV g/ RT @ Where By is calculated with the methods proposed by K.S. Pitzer and R. F. Curl! as well as by J.P. O'Connell and J.M. Prausnitz"". (3) Weight of the stationary liquid It has been found experimentally that losses in stationary liquid with duration of the experimention can be regarded as a being simple lineal relationship WW, = (aw ar o (A) Partition coefficient K"™ KAV/VhPIW, 2, o (5) Equilibrium ratio 07 A=W. ZaRT/M pV 6) (6) Activity coefficient at infinite dilution 7? Y= WZaRT/MV yp? exp, B) b= p/RT J aD (7) Henry's coefficient H H="p) (8) (8) Relative volatility @!, A= TEBE BS = Ving V ar thas te @ (9) Selectivity of solvent 5%, co) 4 CALCULATION RESULTS ‘The partition coefficient K was calculated with adjusted retention time ri scarrier gas flow rate F, at the column outlet (at room temperature) .weight of the stationary liquid W..Wi, and stationary liquid density p, at column temperature whereas the activity cur ficient 7) at infinite dilution was calculated with column temperature 7',column inlet pressure p, and coh umn outlet pressure p,, saturated vapor pressure p? of component i at colin tempera ture. And #? was calculated with the Antoine equation'!"". The calculation results are given in Tables 6—22. ‘Table 6 Dichlorodifluoromethane-acstone ‘Table 7 Chloradifiuoromethane-acctone system at OC system at 0C bkPs Kok 7) HkPa 296.2 14.70 7.28 7.28 2157.47 5.88 585.4 12-49 4.19 7.73 2290.85 5.97 917.7 9.87 27 9.16 2715.48 1173.9 9.42 2.95. 9.45. 2801.77 1465.17.85 2.74 10.22 3090.27 TkPs 358.75 0.72 0.88 An8G 0.54 1.00 487.99 0.50 1.08 S26. 6z 0.15 116 961.87 June, 1998Determination of Thermodynamic Parameters of Some Fluorochlorohydracarbons 179 le 8 Perflerepropens-acete Table 9 Dlchlorediiworomesnane-acerone system a1 OC system a =4C pie K 8 7 Ham @,,, we KOO Wie an Sure 22 6.94 154 14.68 4590.52 12.77 Bohl auf Be ATT GAT BO 0.97 SRGA 5.88 9.19 16.08 So2E.HR 13.05 20.40 S8B.5 S211 Les 3.48 900-26 6.10 TOI 977.7 448 7.30 19.52 6040.98 15.28 980.7 RAL 112 3.55 91LBD 67 LOZ Lm 9 OL 671 0.97 6297.00 13.60 att 7H BEST 08 B81 TOIR0S oer 10.30 M641 3.59 6.00 21.04 6576.97 12.94 21.80 1469.0 2257 0.90 3.78 977.73 6.57 10.56 Table 10 Chlorodituoromethane acetone Toble 11 Petiuoropropene-scetone system at 4 system at — 40 pape RF WAP haya Sig MPs ORF Wik ay Shuey 295-2 198.08 0-54 0.38 161-8) 1 1 585.5 187.26 0.29 0.38 162.79 1 980.7 178.95 0.18 0.58 161-81 1 1 1 wa 4.79 7.27 7.93 2164.30 13.09 20.62 t 3.64 7.17 1955.46 15.19 20.78 1 984.8 12.82 248 7.43 2028-03 1359 21-41 U 1176.8 12.03 2.21 7.53 2054.50 13.73 21-62 1 1467-1 10.76 1.98 7.79 2126-09 11d 22-26 VTA. 8 155.79 0.17 0.41 177.50 1470.0 143.08 0.15 0.43, 183.39 Table 12, Dichloroditooromethane-acetone Table 13. Chlorodituoromethane-cctone system at 86 system at —¥C ihe KF WKPe on rn 7 200.2 G0.87 886 454 1008 BA 10.7 20U2 19085 OSS OM TeLTS 11 see 4 176 G19 965.57 6.36 10.59 6023 I92.78 0.27 0.41 15495 1 075.8 28.26 1-12 4.00 901-24 6.30 10.67 978.7 18.94 GIT O99 MOR 1 1174.8 26.61 0.99 4.09 908.19 6.38 10.66 1172.9 L68.92 0.16 O42 15985 1 I 170.0 25.44 0.88 3.90 877.70 6.43 10.72 L470 _162.51 0.13 0.42 156.8111 Table 14 Perfluoropropene-acetone Octoftuorocyclobutane-acetone system at 80 system at — 9 pate + WAP yon Segag PRP ORF? HAD yu Seen B22 1408 7.55 OAR 2I7G1S 1942 2130 9001 11.08 9.94 26.98 2496.8 20.62 09.74 586.4 14.39 5.88 8.29 1964.28 13.43 2191 5884 1.58 4.55 21.94 2090.0 18.64 75.69 917.7 18-86 2.37 8.02 1896.56 18.69 21-63 582.6 9.39 3.36 21.69 2007.4 0.49 82.96 11748 12.39 2.13 819 1938.77 13.57 21.53 1179.78.69 3.00 21.10 1952.5 16.46 66.86 M749 1161 1808.05 1006.42 13.84 21-95 1470.0 B19 257 18.87 1146.6 19.88 80.75 Table 16 Dichlorediftueromethane-scetone Table 17 Chlorodifuoromethane-ncstone system at —12 system at —120 pire Kb MAPS ay Soggy bkPO ORO Share Zo2 Wai 288 3.80 7439 667 119 29n2 genza OW O38 LIBTO 1 587.4 39.23 1693 2.61 70412 666 LIT 5929 277.76 0.19 0.32 104.99 1 989.6 35.81 0-87 3.54 690.99 6.75 L194 9825 296.03 0.19 0.95. 115.72 1 179 Mas 0.75 44567272 6.66 LIT UN78.9 ZAB.98 0.11 0.34 M108 1 1473.0 38.02 0.63. 3.35 G51 6.92 11.60 LU7I.0 717-44 0.10 0.95 11.76 1 Chinese J. Ch. B. 6(2) 174 1998)180 Chinese J. Ch. F. (Vol. 6. No.2) ‘Table 18 Pertluoroprepene-actone Table 19 DichlorodtIvoromethane-acctone system at —120 system at ~160 Pape OK FY WP yyy Sepmy PP KFT HRP ray, Bae Ves GS 777 WHS 1429 22.75 B9R2 HES DOB 5.01 HHS 7.15 580.4 19.10 2.72 7.05 443.55 14.22 22-74 986-4 38.50 1.35 4168 701-18 7.03 980.7 17.56 1.78 6.86 1405.30 14.52 29:22 979.7 84,1 0.91 4.20 705-08 7.16 1173.9 16.50 1.58 6.92 1416.09 14.12 22.58 1178.8 94.04 0.75 3.97 658.82 7.48, 173.9 15.70 1.32 6.67 1965.09 13.61 21-76 1475.9 20.98 0.66 4.01 674,707.19 Table 20 able 21. erfluoropropene-scetone system at — 160 Faure Fe ee von? pepe 0a? Had 198 GR 7 Dok? TPT AAG VLAD WRIR OP 1ST 24a 589.4 263.22 0.20 0.98 108.85 585.5 17-34 2.99 8.85 1566.32 15.26 24.59 979.7 244.32 0.13 0.38 108.85 6825.27 1178.8 232.81 0.11 0.39 109.84 1477.9 220.94 0.09 0-38 108. 85 1178.8 16-08 1.60 800 1407-26 16.36 26.36 1473.9 14.81 1-38 7.96 1400.40 16-30 26.27 1 1 980-7 16.78 1.84 8.13 1430.80 1 1 1 Table 22 ah, , i eee oe PokPa BokPa 206.2 2189 G01 586.4 2 18l 5825 977.7 2198 980.7 no 2zes 1175.8 165.1 2.240 1469.0 5 CONCLUSIONS The device developed by the author has been proof-tested with CO, in methane-octane sys- tem at 0 and 689kPa. Compared with the literature value of & result of =8. 85 for the equilibrium ratio in the system mentioned above gives a 4.8% rela tive deviation. A series of straight lines can be obtained graphically by plotting Ink vs- 1np yas shown in Fig. 2.As the pressure of the system increases, the & values of F22,F12,C.F,,C.Fy de crease and the solubilities of F22, F12, C.Fs, CF, in acetone increase. On the other hand, the & values of F22,F12,C,F,+C,F, will increase and the solubility of F22,F12Z,C:F,and C,F, in acetone will decrease progressively at the same temperature and pressure. Similarly, a - 45"), our experimental series of straight lines can be obtained by plotting Inai, vs. 1/T',as shown in Fig. 3. The af, values of F12-F22,CsF,-F22 and C.F,-F22 are far above unity. The a, values of F12-F22, C.F.-F22 increase with decreasing temperature. Experimental results proved that in the Production of C.F, with F22 ax raw material and acetone as extractant,it is feasible to have F22,F12,C\F, nd C,F, separated through extraction distillation under low temperature and June, 1998,Determination of Thermodynamic Parameters of Some Fluorochlorehydrocarbons 181 pressurization conditions. The screening and appraisal extractant is also an effective method in chromatography. : ; f 1 SA. z zd aS -| “| a “ : 4 ++ 4 inp, hPo Inp, kPa ta2e rue erm erin ac eras nrin aera +h era. crin scr Five 2 Neate a a et ee epee : : : : : on eee —— ed 2 Fp \ | 1 —_—— —— ae ‘ ‘ a a Serre Sirs Tox 104K-1 To 10K Te to pease wo peur enters nize. ened ntietm ertncty x Fieten seer nereees tose Figure 3 Relallnshps of noo, 1/7 a the sme pressure ACKNOWLEDGEMENTS The author would like to thank the enthusiastic guidance given by Professor Hou Jingdeyof the Department of Chemical Engineering »Zhejiang University. NOMENCLATURE B, second virial coefficient of component i, em?-mol~ Bq second virial coefficient of mixture for sample end carrier gua em?-nol~ Fe mean carrier gas flow rote in column. em?+min-! Fo carrier gas flow rate of column outlet st room temperature, cm?+min™? M, — stationary liquid molecular weight, gemol™! atmospheric pressure at specified, Pa > mean pressure in column, kPa #2 saturated vapor pressure of component ¢ st column tempersture, KP2 fy saturated vapor pressure of water at room tempersture, Pa ‘PivPs column inlet pressure,column outlet pressure, kPa (Chinese J. Cb. . 662) 174 (1998)182 Chinese J. Ch. E. (Vol. 6, No.2) 5 Jemol eK Ro gas conse T.T, column temperature room temperature, K ' overall duration of experimentation at a certain temperature, min 1, adjusted retention time, rin St duration of time from the beginning to » certain moment, min 1, tiguid molecular specifie volume of component £5 ml+mol! Vi molar volume of stationary liguid in column, em?+mol™! Vm molar volume of gas mixtures em?+mol™ Vw net setention volume, em*+mol! Wi weight of stationary liquid in column at Wis weight of stationary liquid in column at ¢=0. g Wis weight of stationary liquid at the end of the experiment, AW differences in weight of ionary liquid from beginning to end, compressibility feetor of min 2, stationary liquid density at columa temperature, geem-* Superscripts © infinite ditation Subscripts 4 component # J component j REFERENCES 1 Hoos J.D.» Wangs LeH. « Analytical Chemistry(China) » 9(5). 524(1981)- 2 Wang. L+H. « Hous J.D. Chen, W.P. , Analytical Chemistry (China), 4001), 26(1982), 3. Wangs LH. y Hous J-D: « Xus N.Q. » Petrochemical Technology (China). 13(1), 14984). 4 Hou, J.D. Wangy L-H. » Huang, F.M. + Zhejiang Chemical Industry (China)+ (4), 2101980). 5 Hou, J-D.. Wangs L-H. « Fan, X.H. « Analytical Chemistry (China), 11(12)- 889(1983). 6 Hou, J.D. , Petrochemicat Technology (China). 12(6) + 361(1989). 7 Beijing Petrochemical General Plant, Zhejiang University. 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