CONFIDENTIAL, = EHIDEC 2013/CHESS3 SS UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION ‘COURSE : CHEMICAL ENGINEERING THERMODYNAMICS COURSE CODE : CHES553 EXAMINATION DECEMBER 2013 TIME 3 HOURS INSTRUCTIONS TO CANDIDATES 1. This question paper consists of five (5) questions. 2 ‘Answer ALL questions in the Answer Booklet. Start each answer on a new page. 3. Do not bring any material into the examination room unless permission is given by the invigitator. 4 Please check to make sure that this examination pack consists of i) the Question Paper ji) aone~page Appendix 1 ii) a.one—page Appendix 2 iv) aone page Appendix 3 v) one ~ page Appendix 4 vi) an Answer Booklet — provided by the Faculty vil) a graph paper — provided by the Faculty DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO This examination paper consists of 4 printed pages: (© Hak Cipta Universit Teknologi MARA CONFIDENTIALCONFIDENTIAL, 2 EHIDEC 2013/CHESS3 QUESTION 1 (P01, PO2, CO1, C2, C4, C5) A binary mixture of methanol (1) / methyl acetate (2) for which methanol liquid mole fraction, x; = 0.55 is in equilibrium with its vapour at 150°C. The activity coefficients (y) of methanol and methyl acetate can be calculated using the following equations Iny, = Ax? Iny, = Ax? where A= 2.771 -0.00523T (T in K) Calculate the equilibrium pressure and vapour composition of the system. Determine whether the system exhibits an azeotrope. (20 marks) QUESTION 2 (P01, PO2, Co2, C1, C4) A researcher reported a series of vapouriliquid equilibrium (VLE) data on mixing process for a binary system of methyl tert-butyl ether (1) / dichloromethane (2) at 308.15 K. The data are given in Table 1. Table 1_VLE data for methyl tert-butyl ether (1) / dichloromethane (2) at 308.15 K Pressure, P (kPa) | Liquid mole fraction, x, | Vapour mole fraction, ys 85.2650 0.0000 0.0000 76.7190 0.1665 - 0.0804 72.4220 0.2482 0.1314 65.0960 0.3880. 0.2457 _ 56.8330 0.5749 0.4564 51.6200 [0.7676 0.7176 49.6240 1.0000 1.0000 a) If the binary system for methyl tert-butyl ether (1) / dichloromethane (2) satisfied modified Raoult’s law, calculate the activity coefficients for both components from the reported experimental data. (8 marks) b) The activity coefficients of the methyl tert-butyl ether (1) / dichloromethane (2) system can be expressed by the Margules equation. With the aid of graph, estimate the values of Margules equation constant, Avz and Az;. Given that co Ber =m, + xaln7y where GF = Excess Gibbs energy, R = Gas constant, T = Temperature, x = Liquid mole fractions and y, = Activity coefficients, for specie: (12 marks) (© Hak Cipta Universiti Teknologi MARA, CONFIDENTIAL,CONFIDENTIAL, 3 EHIDEC 2013/CHESS3 QUESTION 3 (P01, PO2, CO3, C4, C5) Dehydrogenation process of butane takes place at 700°C and 1 bar to produce butane. The reaction is as follows : CaHto(9) + CHe(g) + H2(g) a) Given that the K value is 0.329 at 700°C and the feed stream contains steam and C.H1o ina ratio 12:1, find the conversion of C,Hio at equilibrium, where cal £ = fugacity species i in solution, f°= standard state fugacity, v; = stoichiometric number (12 marks) b) Prove that the conversion of C,H; decrease if the steam is not fed into the system. (6 marks) QUESTION 4 (P01, P02, Co2, C3, C4, C6) 1) Estimate the fugacity of pure n-heptane (liquid) a its normal boiling point and pressure of 250 bar. The molar volume of liquid n-heptane is 163 om*/mol (assumed constant). The fugacity for pure liquid, is given as : SP )=gsPexp eae Fi a) RT o=(oX0'" where ff = Fugacity liquid phase, species i of Saturated fugacity coefficient, species i Pi = Saturated pressure, species i vi Liquid molar volume, species i ¢°.6' = Functions, generalized fugacity coefficient correlation o = Acentric factor (10 marks) (© Hak Cipta Universiti Teknologi MARA, CONFIDENTIAL,CONFIDENTIAL 4 EHIDEC 2013/CHESS3 b) A closed vessel containing a vapor binary mixture of n-heptane and n-hexane is at 300°C and 27 bar. If this vapor consist of 30% (mole) of n-heptane, determine the = i) fugacities of pure-hexane and n-heptane in vapor phase at 300°C and 27 bar. (8 marks) li) fugacities of each of the above component in the vapor mixture at equilibrium. ‘Assume Lewis-Randall rule is valid. (2 marks) QUESTION 5 (P01, PO2, CO2, C2, C4) In atmospheric pressure, acetone (1) and chloroform (2) form an azeotrope that boils at 64.6°C and the mole fraction of acetone in the liquid is 0.335. It is given that the saturation vapor pressures of acetone and chloroform at 64.6°C are 1.31 and 0.98 atm, respectively. a) Calculate the activity coefficients of acetone and chloroform at the azeotrope. (4 marks) b) Using your values in part a), calculate the composition of the vapor over a liquid solution at 64.6°C that contains 12% (mole) acetone. Consider the following Van Laar equations to describe the behavior of this system and note that Iny2_ Acapaye ny: Agy Van Laar equations where 7, Activity coefficients, species i At, Ab) = Infinite dilution values of activity coefficients Liquid mole fraction, species i (16 marks) END OF QUESTION PAPER (© Hak Cipta Universiti Teknologi MARA CONFIDENTIALCONFIDENTIAL APPENDIX 4 EHIDEC 2013/CHES53 Table 1 Constants for the Antoine equation for vapor pressures of pure species InP (kPa = ~ (KT /K +0) Latent heat of vaporization atthe normal boing point (A ,) and normal boiling pont (T,) Parameters for Antoine Equation ‘Temperange Range AH, Ty Name Formula A" _B c K kdimol_K From To ‘Acetone CsHgO 14.3145 275622 45.090 247.15 350.15 9910 329.35 Acetic acid CoH4Oz 15.0717 3580.80 48.500 297.15 415.15 2370 391.05, Acetonitrile® CoH N 14.8950 3413.10 ~22627 246.15 354.15 30.19 35475, Benzene Cole 13.7819 272681 55578 279.15 377.15 30.72 353.15 iso-Butane CaHig 13.8254 2181.79 24.280 190.15 280.15 21.30 261.25, n-Butane CH 13.6608 215470 34.361 20018 292.15 2244 27265, |-Butanol CaHigO 153144 321243 90411 310.15 411.15 43.29 390.75 2-Butanol* CqHigO 15.1989 3026.03 -86.650 298.15 393.15 40.75 372.65 ‘so-Butanol CaHigO 14.6087 2740.95 106480 303.15 401.15 41.82 380.95 tert-Butanol Caio 14.8445 2658.29 -95.500 283.15 374.15 39.07 355.45 Carbon tetrachloride CCly 14.0572 2914.23 41.002 259.15 37415 29.82 349.75 Chlorobenzene CsCl 13.8635 3174.78 61.450 302.15 432.15 35.19 40485 1-Chlorobutane CyHoCl 13.7965 2723.73 $4,885 256.15 35215 30.39 351.65 Chloroform CHC! 13.7324 2548.74 54.598 250.15 357.15 29.24 334.25 Cyclohexane Cobia 13,6568 2723.44 -52.532 282.15 378.15 29.97 353.85, Cyclopentane CsHig 13.9727 2653.90 -38640 238.15 348.15 2730 322.35, n-Decane CioHn 139748 344276 79.202 338.15 476.15 38.75. 447.25 Dichloromethane CHCl 13.9891 2463.93 49.910 235.15 333.15 28.06 31285 Diethyl ether CéHpO 140735 2511.29 -41.950 230.15 328.15 2652 307.55, 14Dioxane CqHyOp 15.0967 3579.78 -32813 293.15 378.15 44.16 37445, n-Bicosane Copter 144,575 4680.46 -141.050 481.15 65215 57.49 616.75 Ethanol CoHgO 168958 3795.17 42.232 276.15 369.15 3856 351.35 Euhylbenzene CeHio 13.9726 325993 -60.850 306.15 436.15 3587 40935, Ethylene glycol* —CzHgO2 15,7567 4187.46 -94.500 373.15 495.15 50.73 47045 n-Heptane CrHig 138622 291026 56.718 277.19 396.15 31.77 37155 n-Hexane CoH 13.8193 2696.04 48.833 254.15 365.15 2885 34185 Methanol CHAO 16.5785 3638.27 -33.650 262.15 356.15 35.21 33785 Methyl acetate CaHgO2 14.2456 2662.78 33.460 250.15 351.15 3032 330.05 Methylethyl ketone CyHgO 14.1334 2838.24 54.460 265.15 376.15 31.30 352.75 Nitromethane* —CHNO2 14.7513 3331.70 —45.550 329.15 419.15 33.99 37435, n-Nonane CoH 13.9854 331119 70456 319.15 451.15 3691 423.95, iso-Octane Cathe 13.6703 289631 $2383 275.18 398.15 30.79 372.35 Octane CaHig 13.9346 3123.13 6351S 299.18 425.15 3441 398.75, nn-Pentane CsHiz 13.7667 2451.88 41.136 22815 331.15 25.79 309.15, Phenol CollgO 14.4387 3507.80 -97.750 353.15 481.15 46.18 45495 |-Propanol CHO 16.1154 3483.67 67.343 293.15 389.15 41.44 370.35, 2-Propanol CHO 16.6796 3640.20 53.540 281.15 37R.15 39.85 355.35, Toluene CyHy 13.9320 305696 55.525 286.15 400.15 33.18 383.75, Water HO 16.3872 3885.70 -42.980 273.15 473.15 40.66 373115, o-Xylene CeHig 140815 3358.79 61.109 313.15 445.15 3624 417.55 m-Xylene CaHig 14.1387 3381.81 57030 308.15 439.15 35.66 412.25, peXylene CyHig 140579 3331.45 58.523 30815 439.15 3567 4114s Based primarily on data presented by B. E, Poling, J. M, Prausnitz and J. P. O'Connell, The Properties of Gases and Liquids, Sth ed., App. A, McGraw-Hill, New York, 2001. “Antoine parameters adapted from Gmehling etal. See footnote 2, p. 791. ***Antoine parameters A are adjusted to reproduce the listed values of Ty (© Hak Cipta Universiti Teknologi MARA CONFIDENTIALCONFIDENTIAL APPENDIX 2 EHIDEC 2013/CHESS3 Table 2 Characteristic properties of pure species Molar Ve mass Te/KPefbar = Ze cm mol“! Tal Methane 16.043 0.012 1906 45.99 0.286 986A. Ethane 30.070 0.100 3053 4872 0.279 «145.5 184.6, Propane 44.097 0.152 3698 4248 0.276 = 200.0 231.1 n-Butane 98.123 0.200 425.1 3796 0.274 255. 272.7 n-Pentane 72.450 0.252 469.7 33.70 0270 313, 309.2, -Hexane 86.177 0301 5076 30.25 0.266 © 371. 341.9 ‘-Heptane 100.204 0350 5402 2740 0261 428, 371.6 n-Ociane 114231 0.400 5687 24.90 0.256 486. 3988, n-Nonane 128258 0.444 5946 22.90 0.252 S44, 424.0 n-Decane 142.285 0492 617.7 21.10 0.247 600. 4473 Isobutane 58.123 0.181 408.1 3648 0.282 262.7 261.4 Isooctane 114231 0302 544.0 25.68 0.266 468. 3724 Cyclopentane 70.134 0.196 S118 45.02 0.273 258. 3224 Cyctohexane 84.161 0.210 5536 40.73 0.273 308, 353.9 Methyleyclopentane 84.161 0.230 5328 37.85 0.272319. 345.0 Methyleyclohexane 98.188 0.235 5722 34.71 0.269 368. 374.1 Ethylene 28.054 0.087 2823 50.40 0.281 131. 169.4 Propylene 42.081 0.140 365.6 46.65 0.289 «1884 225.5 1-Butene 56.108 0.191 4200 4043 0.277 239.3. 266.9. ci 56.108 0.205 435.6 4243 0.273 «2338 = 276.9 36.108 0.218 4286 41.00 0.275 237.7 2740 84.161 0.280 5040 3140 0.265 354, 336.3 Isobutylene 56.108 0.194 4179 40.00 0.275 2389 266.3, 1,3-Butadiene 54.092 0.190 425.2 42.77 0.267 220.4 268.7 Cyclohexene 82145 0.212 5604 4350 0.272 291. 356.1 Acetylene 26.038 0.187 3083 61.39 0271 113. 189.4 Benzene T8114 0.210 5622 4898 0.271 259. 353.2 Toluene 92.141 0.262 S918 41.06 0.264 316. 383.8. Bthylbenzene 106.167 0303 6172 36.06 0.263374. 409.4 ‘Cumene 120.194 0.326 631.1 32.09 0.261 427. 425.6 o-Xylene 106.167 0310 6303 37.34 0.263 369, 417.6 m-Xylene 106.167 0.326 617.1 3536 0.259 376, 4123, Xylene 106.167 0.322 6162 35.11 0.260 379, 41Ls, Styrene 104.152 0.297 6360 3840 0.256 352, 4183, Naptihatene 128.174 0302 7484 ©4051 0.269413, 491.2 Biphenyl 154211 0365 7893 3850 0.295 502. 928.2 Formaldehyde 30.026 0.282 4080 65.90 0.223 115. 254.1 Acetaldehyde 44.053 0.291 466.0: 55.50 0.221 154. 294.0 Methyl acetate 74079 0331 5066 4750 0.257 228, 330.1 Ethyl acetate 88.106 0.366 5233 3880 0.255 286, 350.2 Acetone 58.080 0.307 5082 47.01 0.233209, 320.4 Methyl ethyl ketone 72.107 0.323 535.5 41.50 0.249 267. 3528, Diethyl ether 74123 0.281 466.7 3640 0.263 280. 307.6 Methyl rbutylether 88.150 0.266 497.1 34.30 0.273 329. 3284 (© Hak Cipta Universit Teknologi MARA CONFIDENTIALCONFIDENTIAL APPENDIX 3 EHIDEC 2013/CHESS3 Table 3 Value of 4° P.= 0.0100 0.0500 0.1000 0.2000 0.4000 0.6000 0.8000 1.0000 030 0.0002 0.0000 9.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.35 0.0034 0.0007 0.0003 0.0002 0.0001 0.0001 0.0001 0.0000 0.40 0.0272 0.0055 0.0028 0.0014 0.0007 0.0005 0.0004 0.0003 0.45 0.1321 0.0266 0.0135 0.0069 0.0036 0.0025 0.0020 0.0016 050 04529 0.0912 0.0461 0.0235 0.0122 0.0085 0.0067 0.0055 055 0.9817 0.2432 0.1227 0.0625 0.0325 0.0225 0.0176 0.0146 0.60 0.9840 0.5383 02716 0.1384 0.0718 0.0497 0.0386 0.0321 0.65 0.9886 0.9419 05212 0.2655 0.1374 0.0948 0.0738 0.0611 0.70 0.9908 0.9528 0.9057 0.4560 0.2360 0.1626 0.1262 0.1045 0.75 0.9931 0.9616 09226 0.7178 03715 02559 0.1982 0.1641 0.80 0.9931 0.9683 0.9354 0.8730 0.5445 0.3750 0.2904 0.2404 0.85 0.9954 0.9727 0.9462 0.8933 0.7534 05188 04018 0.3319 0.90 0.9954 0.9772 0.9550 0.9099 08204 06823 05297 0.4375 0.93 0.9954 0.9795 0.9594 0.9183 08375 0.7551 0.6109 0.5058 0.95 0.9954 0.9817 09616 09226 0.8472 0.7709 0.6668 0.5521 0.97 0.9954 0.9817 09638 0.9268 0.8570 0.7852 0.7112 0.5984 0.98 0.9954 0.9817 0.9638 0.9290 0.8610 0.7925 0.7211 0.6223, 0.99 0.9977 0.9840 0.9661 0.9311 0.8650 0.7980 0.7295 0.6442 1.00 0.9977 0.9840 0.9661 0.9333 0.8690 0.8035 0.7379 0.6668 1.01 0.9977 0.9840 0.9683 0.9354 0.8730 08110 0.7464 0.6792 1.02 0.9977 0.9840 0.9683 0.9376 0.8770 08166 0.7551 0.6902 1.05 0.9977 0.9863 0.9705 09441 0.8872 0.8318 0.7762 0.7194 1.10 0.9977 0.9886 0.9750 0.9506 0.9016 0.8531 0.8072 0.7586 LIS 0.9977 0.9886 0.9795 0.9572 09141 0.8730 0.8318 0.7907 1.20 0.9977 0.9908 0.9817 09616 0.9247 0.8892 0.8531 0.8166 1.30 0.9977 0.9931 0.9863 09705 09419 9141 0.8872 0.8590 140 0.9977 0.9931 0.9886 0.9772 0.9550 09333 0.9120 0.8892 1.50 1.0000 0.9954 0.9908 09817 0.9638 0.9462 0.9290 0.9141 1,60 1.0000 09954 0.9931 0.9863 09727 09572 0.9441 0.9311 1.70 1.0000 0.9977 0.9954 0.9886 0.9772 09661 09550 0.9462 1,80 1,000 0.9977 0.9954 0.9908 09817 09727 09661 0.9572 1,90 1.0000 0.9977 0.9954 0.9931 0.9863 09795 09127 0.9661 2.00 1.0000 0.9977 0.9977 0.9954 0.9886 09840 09795 0.9727 2.20 1.0000 1.0000 09977 09977 0.9931 0.9908 0.9886 0.9840 2.40 1.0000 1.0000 1.0000 0.9977 0.9977 09954 0.9931 0.9931 2.60 1.0000 1.0000 1.0000 1,000. 1.0000 09977 09977 0.9977 2.80 1.0000 1,000 1.0000 1.0000 1.0000 1.0000 1.0023 1.0023 3.00 1.0000 1,000 1.0000 1.0000 1.0023 1.0023 1.0046 1.0046 3.50 1.0000 1.0000 1.0000 1.0023 1.0023 1.0046 1.0069 1.0093 4.00 1.0000 1.0000 _1,0000_1.0023__1.0046_ 1.0069 1.0093 _1.0116 (© Hak Cipta Universiti Teknologi MARA CONFIDENTIALCONFIDENTIAL APPENDIX 4 EHIDEC 2013/CHESS3 Table 4 Value of * P= 0.0100 0.0500 0.1000 0.2000 0.4000 _0.6000_0:8000_1.0000_ 7, 030 0.0000 0.0000 0.0000 0.0000 0.0000. 0.0000 0.0000 0.0000 0.35 0.0000 0.0000 0.0000 0.0000 0,0000 0.0000 0.0000 0.0000 0.40 0.9000 0.0000 0.0000 0.0000 0,000 0.0000 0.0000 0.0000 045 0.0002 0.0002 0.0002 0.0002 0.0002 9.0002 0.0002 0.0002 050 0.0014 0.0014 0.0014 0.0014 0.0014 0.0014 0.0013 0.0013 055 0.9705 0.0069 0.0068 0.0068 00066 0.0065 0.0064 0.0063 0.60 09795 0.0227 0.0226 00223 00220 0.0216 00213 0.0210 0.65 0.9863 09311 0.0572 0.0568 00559 0.055! 0.0543 0.0535 0.70 0.9908 0.9528 09036 0.1182 01163 01147 0.1131 0.1116 075 09931 09683 09332 02112 0.2078 02050 0.2022 0.1994 080 09954 09712 09550 09057 03302 03257 0.3212 03168 0.85 0.9977 09863 09705 09375 04774 04708 0.4654 0.4590 0.90 09977 0.9908 09795 0.9594 0.9141 0.6323 0.6250 0.6165 0.93 09977 0.9931 09840 09705 09354 08953 07227 0.7144 095 09977 0.9931 0.9885 09750 0.84 09183 0.7888 0.7797 097 1.0000 0.9954 0.9908 09795 0.9594 09354 0.9078 0.8413 0.98 1.0000 0.9954 0.9908 0.9817 0.9638 09440 0.9225 0.8729 099 1.0000 0.9954 09931 0.9840 0.9683 0.9528 0.9332 0.9036 1.00 1.0000 0.9977 09931 09863 0.9727 0.9594 0.9440 0.9311 1.01 10000 09977 09931 0.9885 0.9772 09638 0.9528 0.9462 1.02 1.0000 0.9977 09954 09908 0.9795 09705 0.9616 0.9572 1.05 1,0000 0.9977 09977 09954 0.9885 0.9863 0.9840 0.9840 1,10 1.0000 1.0000 1,000 1,000 1.0023 1.0046 1.0093 1.0163 1.15 1.0000 1,000 1.0023 1.0046 1.0116 1.0186 1.0257 1.0375 1.20 1.0000 1.0023 1.0046 1.0069 1.0163 1.0280 1.0399 1.0544 130 1.0000 1,023 1.0069 1.0116 1.0257 1.0399 1.0544 1.0716 140 1,000 1.0046 1.0069 1.0139 1.0304 1.0471 1.0642. 1.0815 150 1.0000 1.0046 1.0069 1.0163 1.0328 1.0496 1.0666 1.0865 1.60 1,000 1.0046 1.0069 1.0163 1.0328 1.0496 1.0691 1.0865 1.70 1.0000 1.0046 1.0093 1.0163 1.0328 1.0496 1.0691 1.0865 1.80 1,000 1.0046 1,0069 1.0163 1.0328 1.0496 1.0665 1.0840 1.90 1.0000 1.0046 1.0069 10163 1.0328 1.0496 1.0666 1.0815 2.00 1.0000 1.0046 1.0069 1.0163 1.0304 1.0471 1.0642 1.0815 220 1.0000 1.0046 1.0069 1.0139 1.0304 1.0447 1.0593 1.0765, 240 1.0000 1.0046 1.0069 1.0139 1.0280 1.0423 1.0568 1.0716 2.60 1.0000 1.0023 1.0069 1.0139 1.0257 1.0399 1.0544 1.0666 2.80 1.0000 1.0023 1.0069 1.0116 1.0257 1.0375 1.0496 1.0542 3.00 1.0000 1.0023 1.0069 1.0116 1.0233 1.0352 1.0471 1.0593, 350 1.0000 1.0023 1.0046 1.0023 1.0209 1.0304 1.0423 1.0520 400 1.0000 1.0023 1.0046 1.0093 1.0186__1.0280_1.0375__1.0471. (© Hak Cipta Universiti Teknologi MARA CONFIDENTIAL