APPENDIX I \ Thermochemical Data The data in this appendix have been compiled from a number of sources. Nearly all of the critical property data are taken from Appendix A of The Properties of Gases and Liquids, Second Edition, by R.C. Reid and T.K. Sherwood, copyright © 1966, McGraw-Hill Book Com- pany. They are used with the permission of McGraw-Hill Book Company. Most of the thermochemical data (AG, AH}, and S°) were obtained from the following sources. 1. Zwolinski, B.J., et al., “Selected Values of Properties of Hydrocarbons and Related Compounds,” American Petroleum Institute Research Project 44, Thermodynamics Re- search Center, Texas A&M University, College Station, Texas (Loose-leafdata sheets, extant, 197). 2. Zwolinski, B.J., et al, “Selected Values of Properties of Chemical Compounds,” Ther- modynamics Research Center Data Project, Thermodynamics Research Center, Texas A&M University, College Station, Texas (Loose-Leaf data sheets, extant, 1977). ‘They are used with permission of the Thermo- dynamics Research Center. Other sources used include the Handbook of Chemistry and Physics, STth edition, edited by R. C. Weast, CRC Press, Cleveland, 1974; and Lange’s Handbook of Chemistry, 11th edition, edited by J. A. Dean, McGraw-Hill Book Company, New York, 1973. Absolute Stateof Molecular AGPasc¢ AHS a5. entropy T. P. Compound aggregation weight _—_kcal/g-mole keal/g-mole cal/g-mole-K “Kt Elementary gases Hydrogen Gas 2016 0 0 31.211 333 12.80 Oxygen Gas 32.000 0 0 49.003 «154.8 50.1 Nitrogen Gas 28016 0 0 45.767 126.2335 Fluorine Gas 38.00 0 0 48.6 144,55. Chlorine Gas 7091 0 0 53286417. 76.1 Bromine Liquid 159.83 0 0 364 584,102. Iodine Crystal 253.82 0 0 219 785. 116. Paraffins Methane Gas 1604 — 12140 — 17.889 44.50 190.7 458 Ethane Gas 3007 = 7860 — 20.236 S485 305.4 48.2 Propane Gas 4409 — S614 — 24820 6451 369.9 420 n-Butane Gas 5812 — 410 — 3015 7412 425.2 375 Isobutane Gas 5812 — 500 ~ 3215 70.42 408.1 36.0 n-Pentane Gas MIs — 200 ~ 3500 83.40 469.5 333 2-Methylbutane Gas RIS - 350 — 3692 82.12 460.4 329 Neopentane Gas RIS — 364 — — 3967 73.23 433.8 31.6 n-Hexane Gas 8617 — 007 ~ 39.96 92.83 5073 299 2-Methylpentane Gas 8617 = 120 ~ 41.66 90.95 4965 300 3-Methylpentane Gas 8617 — OSI 41.02 90.77 504.7 308 570Appendix A Thermochemical Data s7 Ske Absolute Stateof Molecular AG. 5 AH} asc entropy T. P. ‘Compound aggregation weight —_kcal/g-mole keal/g-mole cal/g-mole"K °K Atm Olefins Ethylene Gas 28.05 16.282 12.496 52.45 283.1 50.5 Propene Gas 42.08 14.990 4879 63.80 365.1 454 1-Butene Gas 56.10 1709 — 003 73.04 419.6 39.7 cis-2-Butene Gas 56.10 1574 = 167 71.90 4346 40.5 trans-2-Butene Gas 56.10 1505 = 267 70.86 4286 415 Isobutylene Gas 56.10 1388 — 4004 70.17 419.7 39.5 1-Pentene Gas 70.13 1896 — 500 82.65 4648 39.9 cis-2-Pentene Gas 70.13 1117 = 671 82.76 475.6 40.4 trans-2-Pentene Gas 70.13 1676 = 7.59 81.36 475.6 40.4 3-Methyl-I-butene Gas 70.13 1787 = 692 79.70 4648 339 2-Methyl-2-butene Gas 70.13 1426 = 10.17 80.92 470, 34. 1-Hexene Gas 84.16 2094 = — 9.96 91.93 5040 311° 1-Octene Gas 112.21 2496 — 19.82 110.55 S78, 25.5" Cyclopentene Gas 68.11 26.48 787 9.23 506.1 47.2" Diolefins Propadiene Gas 40.06 48.37 4592 58.30 3933 43.6" 1,3-Butadiene Gas 54.09 36.43 26.15 66.62 425, 42.7 Acetylenes. Acetylene Gas 26.04 50.000 54.194 47997 309.5 61.6 Propyne Gas 40.06 46.313 44319 59.30 401. 528 Ethylacetylene Gas 54.09 48.30 39.48 69.51 4637 37.5" Dimethylacetylene Gas 54.09 44.32 3497 67 4887 37.5" Cycloparaffins Cyclopentane Gas 70.13 929° — 1841 70.00 SUL& 446 Methyleyclopentane Gas 84.16 855 — 25.50 81.24 5327 374 Ethyleyclopentane Gas 98.18 1066 © — 3037 90.42 569.5 335 Cyclohexane Gas 84.16 760 — 29.43 11.28 553.2 40. Methyleyclohexane Gas 98.18 652 = 3699 82.06 S721 343 Aromatics Benzene Gas 78.11 30.989 19.820 64.34 562.1 486 Toluene Gas 92.13 29.228 11.950 76.42 5920 41.6 o-Xylene Gas 106.16 29.177 4.540 8431 6316 35.7 m-Xylene Gas 106.16 28.405 4.120 85.49 616.8 347 p-Xylene Gas 106.16 28.952 4.290 84.23 6188 339 Ethylbenzene Gas 106.16 31.208 7.120 86.15 6171 369 Alcohols Methyl alcohol Gas 3204 = 3881 = 48.05 57.29 5132 78.5 Liquid — 3985 — S71 304 Ethyl alcohol Gas 46.07 = 40.13 = 56.03 67.54 5163 630 Liquid — 4165 ~ 66.20 38.53Sos Absolute Stateof Molecular AGPas¢ AH 35-¢ entropy TP Compound aggregation weight keal/g-mole_keal/g-mole cal/g-mole-K = “K Atm n-Propyl alcohol Gas 6009 — 3875 61.33 77.10 5367 51.0 Liquid — 4094 — 72.66 470 Isopropyl alcohol Gas 6009 = 4144 — 65.08 Al 508.2 47.0 Liquid — 4310 — 75.98 43.15 n-Butyl alcohol Gas 7412 36.11 = 65.65 86.92 5630 43.6 Liquid = 3900 7818 545 see-Butyl alcohol Gas 7412 = 4233 — 70.00 858 5360 41.4 Liquid = 40.12 = 81.86 534 tert-Butyl alcohol Gas 7412 — 4245 — 74.68 7792 506.2 39.2 Isobutyl alcohol Gas 7412 = 40.12 = 70.00 858 5477 42.4 Liquid — 4233 — 81.06 534 Phenol Gas 9411 = 761 — 22.98 75.43 694.3 60.5 Liquid = 1217 = 3944 349 Ethers Dimethylether Gas 4607 — 2696 ~ 4399 63.74 400.1 52.6 Diethylether Liquid 7412 = 2932 — 66.83 60.2 4658 35.6 Isopropylether Gas 10217 = 285 — (76.24 912 500.1 284 Liquid — 3009 — 8400 104 Ketones Acetone Gas 5808 = = 3650 ~ 51.79 509.147. Liquid = 3722 = 59.32 Aldehydes Formaldehyde Gas 3003 = 27 — 8 52.26 Acetaldehyde Gas 4405 — 3081 ~ (39.72 598 461. 54.7" Organic Acids Acetic acid Liquid 6005 938 1164 382 5948 57.1 Gas = 9124 = 104.72 Acetic anhydride Gas 10209 -119.29 ~ 148.82 569.2 46.2 Liquid = 12475 = 155.16 Propionic acid Gas 7408 88.27 =108.75 6127 530 Liquid = 9165 121.7 Esters Methyl formate Gas 6005 1137 = 837 29 487.2 59.2 Liquid = 1153 = 90.60 Ethyl acetate Gas 88.10 — 7493 — 102.02 5233 378 Liquid = 7611 —110.72 Ethyl propionate Gas 10213 = 7737 = 11236 546.1 330 Liquid = 79.16 =122.16 ‘Nitrogen compounds Ammonia Gas 1703 = 394 = 11.02 45.97 405.6 112.5 Cyanogen Gas 5202 7081 73.60 57.86 400. 60.0 Hydrogen cyanide Gas 27.03 28.7 312 48.23 456.7 48.9 Methyl amine Gas 3106 + 660 — «67 S173 430.2 BL S72S$se Absolute Stateof Molecular AG?» AH G25 ¢ entropy T. P. ‘Compound aggregation weight _—_keal/g-mole_keal/g-mole cal/g-moleK °K Atm Dimethyl amine Gas 45.08 1635 — 441 65.24 4378 524 Ethyl amine Gas 45.08 1001 = 12.24 4565 55.5 Propyl amine Gas 59.11 1438 — 16.45 497 468 Nitro methane Liquid 6104 = 226 — 21.28 au 588) 623 Sulfur compounds Sulfur Crystal 32.06 0 0 7.62 1313. 116. Carbonyl sulfide Gas 60.07 = 4085 ~ 3383 378.65. Carbon disulfide Gas 76.13 15.55 21.55 56.84 552.78. Liquid 152 210 36.10 Hydrogen sulfide Gas 3408-7892 4.815 49.15 3736 88.9 Dimethyl sulfide Gas 62.13 37 = 69 68.28 503.1 546 Methyl mercaptan Gas 4810 — 223 — S34 60.90 470.714 Inorganic halides Hydrogen fluoride Gas 201 - 647 642 41.47 461. 6424 Hydrogen chloride Gas 36.49 — 22.769 — 22.063 44617 3246 821 Hydrogen bromide Gas 8092 - 1272 = 8.66 41.437 3632 84.5 Hydrogen iodide Gas 127.93 031 620 49314 4242819 Organic halides Methyl chloride Gas 5049 140 ~ 196 5597 4163 659 Methyl bromide Gas 9495 = 62 9 - 8S 58.74 4672 83.4" Methyl iodide Gas 141.95 53 49 60.85 528, 72.7 Methylene chloride Gas 8994 — 14, re 64.68 510. 60. Chloroform Gas 11939 = 16. - 4 10.86 5366 54. Liquid -1m - 318 48.5 Carbon tetrachloride Gas 15384 — 153 25.50 73.95 5564 450 Liquid - 164 9 ~ 333 51.25 Ethyl chloride Gas 64520 127 = 28 6590 4604 520 12-Dichloroethane Liquid 9897-192 — 39.7 49.84 561 Onides Carbon dioxide Gas 4401 — 94.2598 — 940518 51.061. 3042729 Carbon monoxide Gas 28.01 = 328077 — 264157 47300133. 345 Ethylene oxide Gas 4405-279 1219 58.1 468. 71.0 Nitrous oxide Gas 44.02 24.76 19.49 52.58 309.777 Nitric oxide Gas 30.01 20.719 21.600 50339 «180.64, Nitrogen dioxide Gas 46.01 12390 8.091 $1.47 431. 100. Sulfurdioxide Gas 6406 = — 71.79 — 70.96 59.40 4307777 Sulfur trioxide Gas 80.06 — 8852 — 94.45 61.24 4914 814 Water Gas 1802 = 546351 — 57.7979 45.106 647.2183, Liquid = 56.6899 — 68.3174 16.716 "Calculated by Lydersen’s Critical Property Method, Reid and Sherwood, The Properties of Gases and Liquids, Second Edition, McGraw-Hill, 1966, Table 2-1, p. 9. 573,=~. Generalized Fugacity Coefficients of Pure Gases and Liquids (Z,=0.27) Reduced pressure, P, 15% 02 03 0405 10 203.0 40 50 10 23040 60 T T | T Fugacity coefficient, /P eS [ona o 01 0203 04 05 70 20 30 4050 70 20 3040 50 Reduced plessure, P, \ (Reprinted from Chemical Process Principles Charts, Third Edition, by 0. A. Hougen, K. M. Watson, and R. A. Ragatz. Copyright 1964. Reprinted by permission of John Wiley and Sons, Inc.) 314 Fugacity coefficient, 7?