Appendix A Critical Constants and Acentric Factors

Compiled from 1. NIST (National Institute of Standards and Technology) Chemistry WebBook www.nist.gov/chemistry 2. Korea Thermophysical Properties Data Bank (KDB) www.cheric.org/research/kdb

517

Name

Formula

Molecular Weight ELEMENTS

Tc ( K)

Pc ( MPa)

Bromine Chlorine Hydrogen Iodine Neon Nitrogen Oxygen

Br2 Cl2 H2 I2 Ne N2 O2

159.81 70.91 2.02 253.81 20.18 28.01 32.00

588.0 417.0 33.2 819.0 44.4 126.2 154.6

10.34 7.99 1.30 11.65 2.76 3.40 5.04

0.108 0.090 0.216 0.029 0.229

0.039 0.025

HYDROCARBONS Acetylene Benzene n-Butane Cumene Cyclohexane Cyclopentane n-Decane Ethane Ethylbenzene Ethylene n-Heptane 1-Heptene n-Hexane 1-Hexene Isobutane Isopentane Methane Naphthalene n-Octane 1-Octene n-Pentane Propane Propylene Styrene Toluene m-Xylene o-Xylene p-Xylene C2 H2 C6 H6 C4 H10 C9 H12 C6 H12 C5 H10 C10 H22 C2 H6 C8 H10 C2 H4 C7 H16 C7 H14 C6 H14 C6 H14 C4 H10 C5 H12 CH4 C10 H8 C8 H18 C8 H16 C5 H12 C3 H8 C3 H6 C8 H8 C7 H8 C8 H10 C8 H10 C8 H10 26.04 78.11 58.12 120.19 84.16 70.13 142.28 30.07 106.17 28.05 100.20 98.19 86.18 84.16 58.12 72.15 16.04 128.17 114.23 112.21 72.15 44.10 42.08 104.15 92.14 106.17 106.17 106.17 308.3 562.0 425.0 631.0 554.0 511.7 617.8 305.3 617.0 282.5 540.0 537.3 507.6 504.0 407.7 461.0 190.6 748.0 568.9 567.0 469.8 369.9 365.2 647.0 593.0 618.0 631.0 617.0 6.14 4.89 3.80 3.21 4.07 4.51 2.11 4.90 3.64 5.06 2.74 2.92 3.02 3.21 3.65 3.38 4.61 4.10 2.49 2.68 3.36 4.25 4.60 3.99 4.10 3.54 3.70 3.50 0.190 0.212 0.199 0.326 0.212 0.196 0.489 0.099 0.302 0.089 0.349 0.358 0.299 0.285 0.183 0.227 0.011 0.302 0.398 0.386 0.251 0.153 0.144 0.257 0.263 0.325 0.310 0.320

518

Name

Formula

Molecular Weight

Tc ( K)

Pc ( MPa)

INORGANIC COMPOUNDS Ammonia Carbon dioxide Carbon disulde Carbon monoxide Carbon tetrachloride Chloroform Hydrogen chloride Hydrogen cyanide Hydrogen sulde Nitric oxide Nitrous oxide Sulfur dioxide Sulfur trioxide Water NH3 CO2 CS2 CO CCl4 CHCl3 HCl CHN H2 S NO N2 O SO2 SO3 H2 O 17.03 44.10 76.14 28.01 153.82 119.38 36.46 27.03 34.08 30.01 44.01 64.06 80.06 18.02 405.4 304.2 552.0 134.5 556.4 537.0 324.7 456.7 373.3 180.0 309.6 430.3 491.0 647.0 11.30 7.38 7.90 3.50 4.49 5.33 8.26 5.39 8.97 6.48 7.24 7.88 8.20 22.06 0.250 0.239 0.109 0.066 0.193 0.218 0.133 0.388 0.081 0.588 0.165 0.256 0.481 0.344

ORGANIC COMPOUNDS Acetaldehyde Acetic acid Acetone Acetonitrile Aniline n-Butanol Chlorobenzene Diethyl ether Dimethyl ether Ethanol Ethyl acetate Ethylene oxide Formaldehyde Furfural n-Heptanol Isobutanol Isopropanol Methanol Methyl acetate Methyl ethyl ketone Phenol n-Propanol C2 H4 O C2 H4 O2 C3 H6 O C2 H3 N C6 H7 N C4 H10 O C6 H5 Cl C4 H10 O C2 H6 O C2 H6 O C4 H8 O2 C2 H4 O CH2 O C5 H4 O2 C7 H16 O C4 H10 O C3 H8 O CH4 O C3 H6 O2 C4 H8 O C6 H6 O C3 H8 O 519 44.05 60.05 58.08 41.05 93.13 74.12 112.56 74.12 46.07 46.07 88.11 44.05 30.03 96.08 116.20 74.12 60.10 32.04 74.08 72.11 94.11 60.10 466.0 593.0 508.0 545.0 698.8 562.0 632.4 467.0 401.0 514.0 530.0 468.9 408.0 670.0 632.6 548.0 509.0 513.0 510.0 535.0 694.3 536.9 5.57 5.78 4.80 4.87 5.31 4.50 4.52 3.60 5.40 6.30 3.88 7.23 6.59 5.51 3.06 4.50 4.90 8.10 4.75 4.20 5.93 5.20 0.303 0.447 0.304 0.327 0.384 0.593 0.249 0.281 0.200 0.644 0.362 0.202 0.253 0.383 0.560 0.592 0.665 0.556 0.326 0.320 0.438 0.623

520

Appendix B Heat Capacity of Ideal Gases

Compiled from 1. Korea Thermophysical Properties Data Bank (KDB) www.cheric.org/research/kdb

The heat capacity is expressed as a function of temperature in the form

eP = a + bT + cT2 + dT3 + eT4 C

e is in J/ mol. K and T is in K. The coecients are valid for 200 K T 800 K. where C P

521

Name

b 101 0.113 0.340 0.119 0.065 0.070 0.099 1.764 6.267 2.335 8.017 6.444 5.809 0.111 0.759 0.751 0.692 3.941 4.001 3.447 2.091 4.159 0.511 7.213 4.810 4.544 2.485 0.838 1.478 7.580 4.800 6.354 5.660 6.734

c 104 0.119 0.373 0.241

d 107 453.400 0.159 0.215 0.028 0.085 0.339 1.689 2.799 2.437 1.643 1.020

e 1011 0 0.172 0 0.615 0.093 0.918

ELEMENTS Bromine Chlorine Hydrogen Iodine Nitrogen Oxygen 33.860 26.468 27.004 35.590 29.802 29.705

0.070

0.174 0.399

HYDROCARBONS Acetylene Benzene n-Butane Cumene Cyclohexane Cyclopentane n-Decane Ethane Ethylbenzene Ethylene n-Heptane 1-Heptene n-Hexane Isobutane Isopentane Methane Naphthalene n-Octane 1-Octene n-Pentane Propane Propylene Styrene Toluene m-Xylene o-Xylene p-Xylene 8.709 60.711 24.258 5.795 2.419 1.279 4.437 5.493 1.346

8.552 3.796

42.658

63.733 61.877 121.188 33.313 39.308 17.562 37.663 28.940 32.365 24.108 4.817 36.155

5.444

2.633 3.631 23.586 3.566 11.746 0.936 2.587 1.935 2.026 2.166

0.378 32.069 16.549

134.425 11.983 67.943 4.294 16.635 16.620 13.306 11.619 4.688 4.899 4.422 18.845 20.411 12.977 13.129 4.845 7.005 5.445

0.770

3.762 1.293

4.744 4.420 3.806

0.809 3.873

3.372

2.215

1.008 1.824 0.012

47.760

37.209 33.168 33.780

2.419 2.477 2.535

5.167 5.425 3.958 1.384 3.838

29.595 17.905 51.641 20.488

3.256 68.773 6.943 3.678 2.796 1.636

3.422 0.687 0.203 1.133

33.289 39.704 12.618

0.887

0.750 1.721 0.380

4.317

522

Name

b 101 0.221 0.813

c 104 1.213 2.653 0.767 2.270 1.841 0.026 0.183

d 107 1.088 0.267

e 1011 3.203 20.057 0 0.108 0 0 0.408 0 0.860 1.418 2.347 3.244 0 0.110

INORGANIC COMPOUNDS Ammonia Carbon dioxide Carbon disulde Carbon monoxide Carbon tetrachloride Chloroform Hydrogen chloride Hydrogen iodide Hydrogen sulde Nitric oxide Nitrous oxide Sulfur dioxide Sulfur trioxide Water 34.236 29.268 27.440 29.651 40.720 24.000 29.179 31.160 33.876 34.152 51.060 31.666 19.210 33.763 0.224 0.007 4.153 0.094

2.049 1.893

0.884 0.666 0.093

0.002

0.143 0.119

0.297 0.538

0.135 0.541 0.377

0.512

0.310

0.708 1.154 0.703 1.176 0.224

0.142

1.374 0.006 1.823 2.549 2.606 1.196 6.385 3.460 5.631 2.467 1.791 1.428 4.072 2.222 0.316 6.778 4.689 2.088 0.134 2.245 1.881 5.545 2.216

0.931

0.887

0.370

0.100 0.238 0.495 0.204 0.032 1.633 1.515 2.084 1.426

ORGANIC COMPOUNDS Acetaldehyde Acetic acid Acetone Acetonitrile Aniline n-Butanol Chlorobenzene Diethyl ether Dimethyl ether Ethanol Ethyl acetate Ethylene oxide Formaldehyde n-Heptanol Isobutanol Isopropanol Methanol Methyl acetate Methyl ethyl ketone Phenol n-Propanol 7.716 4.840 6.301 20.480 40.520 33.890 11.707 1.007 0 0 0 0 0 6.499 0 6.953 0 5.366 0 0 0 0 0 8.683 6.212 0 6.926 0.685 6.408 1.753

1.253

0.449 5.133

39.252

4.522 0.523 2.092

0.251

1.055

17.020 19.959 7.235 7.519 23.480

0.776

1.513

0.019

0.286 0.259

1.256

0.299

49.070 7.708 24.208

3.447

0.230

0.605 0.723

2.884

1.035

34.375 16.550 41.846 27.718 18.884

2.156 0.434 4.151 1.212

2.090 2.057 1.733

2.322 0.291

1.277

0.618

523

524

Appendix C Antoine Constants

Compiled from 1. R.C. Reid, J.M. Prausnitz and T.K. Sherwood, The Properties of Gases and Liquids, 3rd Ed., McGraw-Hill, New York, 1977.

The vapor pressure is expressed as a function of temperature in the form ln P vap = A where P vap is in bar and T is in K. B T +C

525

Name

B ELEMENTS

Tmax

Tmin

Argon Bromine Chlorine Hydrogen Nitrogen Oxygen

8.6128 9.2239 9.3408 7.0131 8.3340 8.7873

700.51 2582.32 1978.32 164.90 588.72 734.55

27.01 3.19 6.60

51.16

5.84

94 354 264 25 90 100

81 259 172 14 54 63

6.45

HYDROCARBONS Acetylene Benzene n-Butane Cumene Cyclohexane Cyclopentane n-Decane Ethane Ethylbenzene Ethylene n-Heptane 1-Heptene n-Hexane Isobutane Isopentane Methane Naphthalene n-Octane 1-Octene n-Pentane Propane Propylene Styrene Toluene m-Xylene o-Xylene p-Xylene 9.7279 9.2806 9.0580 9.3520 9.1325 9.2372 9.3912 9.0435 9.3993 8.9166 9.2535 9.2692 9.2164 8.9179 9.0136 8.6041 9.5224 9.3224 9.3428 9.2131 9.1058 9.0825 9.3991 9.3935 9.5188 9.4954 9.4761 1637.14 2788.51 2154.90 3363.60 2766.63 2588.48 3456.80 1511.42 3279.47 1347.01 2911.32 2895.51 2697.55 2032.73 2348.67 597.84 3992.01 3120.29 3116.52 2477.07 1872.46 1807.53 3328.57 3096.52 3366.99 3395.57 3346.65 52.36 19.77 202 377 290 454 380 345 476 199 450 182 400 400 370 280 322 120 525 425 420 330 249 240 460 410 440 445 440 194 280 195 311 280 230 330 130 300 120 270 265 245 187 216 93 360 292 288 220 164 160 305 280 300 305 300

63.37

34.42

33.15 40.05 7.16

48.78

53.97

56.51

18.15

59.95

17.16

78.67

41.79

50.50

63.72

26.15

25.16

39.94

60.39

63.63

71.29

58.04 57.84 59.46

53.67

526

Name

Tmax

Tmin

INORGANIC COMPOUNDS Ammonia Carbon dioxide Carbon disulde Carbon monoxide Carbon tetrachloride Chloroform Hydrogen chloride Hydrogen sulde Nitric oxide Nitrous oxide Sulfur dioxide Sulfur trioxide Water 10.3729 15.9696 9.3642 7.7484 9.2540 8.3530 9.8838 9.4838 13.5112 9.5069 10.1478 14.2201 11.6834 2132.50 3103.39 2690.85 530.22 2808.19 2696.79 1714.25 1768.69 1572.52 1506.49 2302.35 3995.70 3816.44 32.98 31.62 0.16 261 204 342 108 374 370 200 230 140 200 280 332 441 179 154 228 63 253 260 137 190 95 144 195 290 284

13.15 45.99 46.16 14.45 4.88

26.06

46.13 37.15

36.66

35.97

25.99

ORGANIC COMPOUNDS Acetaldehyde Acetic acid Acetone Acetonitrile Aniline n-Butanol Chlorobenzene Diethyl ether Dimethyl ether Ethanol Ethyl acetate Ethylene oxide Formaldehyde n-Heptanol Isobutanol Isopropanol Methanol Methyl acetate Methyl ethyl ketone Phenol n-Propanol 9.6729 10.1878 10.0311 9.6672 10.0546 10.5958 9.4474 9.4626 10.2265 12.2917 9.5314 10.1198 9.8573 8.6866 10.2510 12.0727 11.9673 9.5093 9.9784 9.8077 10.9237 2465.15 3405.57 2940.46 2945.47 3857.52 3137.02 3295.12 2511.29 2361.44 3803.98 2790.50 2567.61 2204.13 2626.42 2874.73 3640.20 3626.55 2601.92 3150.42 3490.89 3166.28 320 430 350 390 500 404 420 340 265 369 385 310 271 449 388 374 364 360 376 481 400 210 290 241 260 340 288 320 225 179 270 260 200 185 333 293 273 257 245 257 345 285 56.34

35.93 73.15

49.15

94.43

55.60 41.95

41.68 29.01 146.6 30.15

17.10

57.15

53.54

100.3

34.29 56.15 36.65

80.15

98.59

527

528

Appendix D Corresponding States Using the Lee-Kesler Equation of State1

At a given temperature and pressure, rst determine the reduced temperature and pressure Tr = T Tc and Pr = P Pc (D-1)

Compressibility Factor
er(0) be the ideal reduced volume of a simple uid, i.e., = 0. The value of V er(0) is estimated Let V from the solution of the following equation " # " # er(0) Pr V B C D c4 = 1 + (0) + + + + exp (0) (D-2) 3 (V Tr er(0) )2 (V er(0) )5 Tr er(0) )2 er(0) )2 er )2 er (V (V (V V b2 Tr c2 + C = c1 Tr d2 D = d1 + Tr B = b1 b3 b4 3 2 Tr Tr c3 3 Tr (D-3) (D-4) (D-5)

where

and the constants are given in Table D.1 for a simple uid. Table D.1 Constants in Eq. (D-2). Constants b1 b2 b3 b4 c1 c2 c3 c4 d1 104 d2 104 Simple Fluid 0.1181193 0.265728 0.154790 0.030323 0.0236744 0.0186984 0 0.042724 0.155488 0.623689 0.65392 0.060167 Reference Fluid 0.2026579 0.331511 0.027655 0.203488 0.0313385 0.0503618 0.016901 0.041577 0.48736 0.0740336 1.226 0.03754

er(0) is determined, the value of Z (0) is calculated as Once V Z (0)

1

er(0) Pr V = Tr

(D-6)

Lee, B.I. and M.G. Kesler, 1975, AIChE Journal 21, 510-525.

529

er(0) in Eq. (D-2) is replaced by V er(R) together with the For a reference uid, the term V er(R) is determined from the solution reference uid constants in Table D.1. Once the value of V of Eq. (D-2), the value of Z (R) is calculated from Z (R) = Then, the value of Z (1) is given by Z (1) = er Pr V Tr
(R)

(D-7)

Z (R) Z (0) 0.3978

(D-8)

Enthalpy Departure Function

For a simple uid (0) IG e e H H RTc " 1 2 b3 3 b4 3 c3 b2 + c2 2 + 2 Tr Tr Tr er(0) )2 2 Tr (V # d2 + 3 Eo + (D-9) er(0) )5 5 Tr (V er )2 (V
(0)

T,P

= Tr Z

(0)

1 1 er(0) Tr V ( "

where c4 Eo = 3 2 Tr For a reference uid (R) e H e IG H RTc "

+1 +1+

exp

"

er )2 (V

(0)

#)

(D-10)

T,P

= Tr Z (R) 1

1 (R) e Tr Vr "

where c4 ER = 3 2 Tr

1 2 b3 3 b4 3 c3 b2 + c + 2 2 2 Tr Tr Tr er(R) )2 2 Tr (V # d2 + 3 ER + (D-11) er(R) )5 5 Tr (V er (V

(R) 2 )

+1 +1+

exp

"

(1) e H e IG /RTc is given by Then, the value of H

T,P

er (V

(R) 2 )

#)

(D-12)

(1) e H e IG H RTc

T,P

(R) (0) IG IG e H e e H e H H 1 T,P T,P = 0.3978 RTc RTc

(D-13)

530

Entropy Departure Function

For a simple uid (0) eS eIG S R b3 2 b4 2 c3 1 b1 + 2 + 3 c1 3 Tr Tr Tr er(0) )2 2 (V d1 + 2 Eo (D-14) er(0) )5 5 (V b3 2 b4 2 c3 1 b1 + 2 + 3 c1 3 Tr Tr Tr er(R) )2 2 (V d1 + 2 ER (D-15) er(R) )5 5 (V

T,P

= ln Z

(0)

1 (0) er V

For a reference uid (R) IG e e SS R 1

T,P

= ln Z

(R)

er(R) V

(1) eS eIG /R is given by Then, the value of S

T,P

(1) eS eIG S R

T,P

(R) (0) IG IG eS e eS e S S 1 T,P T,P = 0.3978 R R

(D-16)

531

532

Appendix E Enthalpy and Gibbs Energy of Formation at 298 K and 1 bar

Compiled from 1. NIST (National Institute of Standards and Technology) Chemistry WebBook www.nist.gov/chemistry 2. Korea Thermophysical Properties Data Bank (KDB) www.cheric.org/research/kdb

533

Name

Formula

Phase

Acetylene Benzene Benzene n-Butane Cumene Cyclohexane Cyclohexane n-Decane n-Decane Ethane Ethylbenzene Ethylbenzene Ethylene n-Heptane n-Heptane n-Hexane n-Hexane 1-Hexene Isobutane Isobutane Isopentane Methane Naphthalene Naphthalene n-Octane n-Octane 1-Octene 1-Octene n-Pentane n-Pentane Propane Propylene Styrene Toluene Toluene m-Xylene m-Xylene o-Xylene o-Xylene p-Xylene p-Xylene

HYDROCARBONS C2 H2 G 226.90 C6 H6 C6 H6 C4 H10 C9 H12 C6 H12 C6 H12 C10 H22 C10 H22 C2 H6 C8 H10 C8 H10 C2 H4 C7 H16 C7 H16 C6 H14 C6 H14 C6 H12 C4 H10 C4 H10 C5 H12 CH4 C10 H8 C10 H8 C8 H18 C8 H18 C8 H16 C8 H16 C5 H12 C5 H12 C3 H8 C3 H6 C8 H8 C7 H8 C7 H8 C8 H10 C8 H10 C8 H10 C8 H10 C8 H10 C8 H10 G L G G G L G L G G L G G L G L G G L G G G S G L G L G L G G G G L G L G L G L 534 82.98 48.95 126.2 123.20 157.70 249.80 301.00 3.94

eo H f ( kJ/ mol)

eo G f ( kJ/ mol) 209.30 129.70 124.53 16.10 31.78 26.89 33.24 17.25 32.95 130.7 119.95 68.16 8.00 1.33 0.17 4.04 87.50 20.90 21.98 14.82 50.87 223.7 201.18 16.40 6.71 104.3 94.16 8.37 9.46 62.76 213.9 122.1 113.96 118.9 107.73 122.20 110.76 121.20 110.03 137.10

29.81 12.47 52.34 187.90 224.39 167.30 198.78 134.60 158.55 154.60

84.74

41.70

74.90 151.1 78.13

208.6 249.95 82.98 123.59 146.5 173.33 103.9 20.43 147.5 50.03 12.01 17.25 25.41 19.00 24.39 17.96 24.45

23.49

Name

Formula

Phase

INORGANIC COMPOUNDS Ammonia Calcium carbonate Calcium chloride Calcium chloride Calcium hydroxide Calcium oxide Calcium sulfate Carbon dioxide Carbon disulde Carbon monoxide Carbon tetrachloride Chloroform Chloroform Hydrogen chloride Hydrogen cyanide Hydrogen iodide Hydrogen sulde Nitric oxide Nitrogen dioxide Nitrous oxide Dinitrogen tetroxide Dinitrogen tetroxide Sodium carbonate Sodium chloride Sodium hydroxide Sodium hydroxide Sulfur dioxide Sulfur trioxide Sulfuric acid Sulfuric acid Tungsten Tunsten dioxide Tunsten dioxide Water Water Zinc oxide Zinc sulfate Zinc sulde NH3 CaCO3 CaCl2 CaCl2 Ca(OH)2 CaO CaSO4 CO2 CS2 CO CCl4 CHCl3 CHCl3 HCl HCN HI H2 S NO NO2 N2 O N2 O4 N2 O4 Na2 CO3 NaCl NaOH NaOH SO2 SO3 H2 SO4 H2 SO4 W WO2 WO2 H2 O H2 O ZnO ZnSO4 ZnS G S G S S S S G G G L G L G G G G G G G G L S S G S G G G L G G S G L S S S

eo H f ( kJ/ mol) 45.72

eo G f ( kJ/ mol) 16.16

1206.92 471.54 795.80 986.09 634.92

1128.81 479.15 748.11 603.51 898.47

1434.11 393.80 117.10

1321.68 394.60 66.95 137.40 68.58 71.89 120.20 1.59 33.08 86.75 51.26 103.70 97.79 97.51 1048.01 384.02 200.19 379.74 65.20

110.60

101.30 134.30 92.36 130.60 26.38 20.18 90.43 33.1 81.60 9.08 19.56

128.40

95.30

1130.77 197.76 425.93 411.12

297.10 396.00

300.40 371.30

735.13 813.99 851.03 76.57 589.69

653.37 689.89 808.90 62.36 533.86

242.00 285.83 350.46 205.98

228.80 237.14 320.48 201.29

980.14

871.45

535

Name

Formula

Phase

ORGANIC COMPOUNDS Acetaldehyde Acetic acid Acetic acid Acetone Acetone Acetonitrile Acetonitrile Aniline Aniline n-Butanol n-Butanol Ethanol Ethanol Ethyl acetate Ethyl acetate Ethylene oxide Ethylene oxide Formaldehyde n-Heptanol Isobutanol Isopropanol Methanol Methanol Methyl ethyl ketone Phenol Phenol n-Propanol n-Propanol C2 H4 O C2 H4 O2 C2 H4 O2 C3 H6 O C3 H6 O C2 H3 N C2 H3 N C6 H7 N C6 H7 N C4 H10 O C4 H10 O C2 H6 O C2 H6 O C4 H8 O2 C4 H8 O2 C2 H4 O C2 H4 O CH2 O C7 H16 O C4 H10 O C3 H8 O CH4 O CH4 O C4 H8 O C6 H6 O C6 H6 O C3 H8 O C3 H8 O G G L G L G L G L G L G L G L G L G G G G G L G G S G L

eo H f ( kJ/ mol) 164.40

eo G f ( kJ/ mol) 133.40

435.10 484.09 217.70 248.11

376.90 389.23 153.20 155.26

87.92 53.17 86.92 31.11

105.7 98.93

166.80 149.18 150.90 161.19

274.90 326.03

443.20 479.86

235.00 276.98

332.00 283.40

116.00

52.67 77.46

327.60 332.93

168.40 173.99

121.00 167.40

110.00

13.10 11.43

272.60

238.50

201.30 238.57

173.50

96.42 165.02 256.60 304.76

146.20

162.60 166.15 32.90 50.22

161.90 170.78

536

Appendix F Matrices

F.1

MATRIX DEFINITION

The numbers or functions aij are called the elements of a matrix. Equation (F.1-1) is also expressed as (F.1-2) A = (aij ) in which the subscripts i and j represent the row and the column of the matrix, respectively. A matrix having only one row is called a row matrix (or row vector ) while a matrix having only one column is called a column matrix (or column vector ). For example, b = b1 b2 b3 ... bn Row matrix (row vector) (F.1-3) b1 b2 Column matrix (column vector) (F.1-4) b= ..... bm For convenience in writing, the elements of a one-column matrix are frequently arranged horizontally, i.e., (F.1-5) b = b1 b2 b3 ... bn The use of braces then being necessary to indicate the transposition. F.2 TYPES OF MATRICES

A rectangular array of elements or functions is called a matrix. If the array has m rows and n columns, it is called an m n matrix and expressed in the form a11 a12 a13 ... a1n a21 a22 a23 ... a2n (F.1-1) A= ..... ..... ..... ... ..... am1 am2 am3 ... amn

Square Matrix When the number of rows and the number of columns are the same, i.e., m = n, the matrix is called a square matrix or a matrix of order n. For example, a11 a12 a13 A = a21 a22 a23 (F.2-1) a31 a32 a33

In a square matrix, the diagonal containing elements of equal indices (a11 , a22 , ..., ann ) is called the principal diagonal of this matrix. Diagonal Matrix A square matrix in which all the elements except those on the major diagonal line are zero, is called a diagonal matrix. For example, 537

A diagonal matrix in which the diagonal elements identity matrix, I, i.e., 1 0 I = 0 1 0 0 Triangular Matrix

0 a11 0 A = 0 a22 0 0 0 a33 0 0 1

(F.2-2)

are all unity is called the unit matrix or the

(F.2-3)

A matrix having all elements on one side of the major diagonal line are zero is called a triangular matrix. If zero elements are below the major diagonal line, then the matrix is called an upper tridiagonal matrix, U. If zero elements are above the major diagonal line, then the matrix is called a lower tridiagonal matrix, L, i.e., 0 a11 0 a11 a12 a13 L = a21 a22 0 (F.2-4) U = 0 a22 a23 0 0 a33 a31 a32 a33 Sparse Matrix A matrix in which most elements are zero is called a sparse matrix. Null Matrix A matrix whose elements are all zero is called a null matrix and is denoted by 0. F.3 MATRIX ALGEBRA

F.3.1 Addition and Subtraction If A = (aij ) and B = (bij ) have the same order, the sum of A and B is dened as A + B = (aij + bij ) (F.3-1)

If A, B, and C are the matrices of the same order, addition is commutative and associative, i.e., A+B=B+A (F.3-2) A + (B + C) = (A + B) + C (F.3-3)

If A = (aij ) and B = (bij ) have the same order, the dierence of A and B is dened as A B = (aij bij ) (F.3-4)

Example F.1 If

determine A + B and A B.

2 1 2 4 0 and B = 3 0 A= 1 3 5 0 1 538

Solution The use of Eq. (F.3-1) gives 2 + 2 1 4 4 5 0 + 0 = 4 0 A + B = 1 + 3 3+0 5+1 3 6 3 0 4

Application of Eq. (F.3-4) yields

2 2 1 + 4 0 A B = 1 3 0 0 = 2 30 51 3 F.3.2 Multiplication Scalar multiplication

If A = (aij ) and is any number, the product of A by is dened as A = A = ( aij ) Example F.2 If 2 1 A= 3 5 determine 2A B. Solution 2 1 1 1 (2)(2) 1 (2)(1) + 1 3 3 2A B = 2 = = 3 5 4 2 (2)(3) 4 (2)(5) 2 2 8 Matrix multiplication The product of two matrices A and B, A B, is dened only if the number of columns in A is equal to the number of rows in B. In this case, the two matrices are said to be conformable in the order stated. For example, if A is of order (4 2) and B is of order (2 3), then the product A B is a11 a12 a21 a22 b11 b12 b13 AB = a31 a32 b21 b22 b23 a41 a42 a11 b11 + a12 b21 a11 b12 + a12 b22 a11 b13 + a12 b23 a21 b11 + a22 b21 a21 b12 + a22 b22 a21 b13 + a22 b23 (F.3-6) = a31 b11 + a32 b21 a31 b12 + a32 b22 a31 b13 + a32 b23 a41 b11 + a42 b21 a41 b12 + a42 b22 a41 b13 + a42 b23 In general, if a matrix of order (m r) is multiplied by a matrix of order (r n), the product is a matrix of order (m n). Symbolically, this may be expressed as (m r)(r n) = (m n) 539 1 1 and B = 4 2 (F.3-5)

(F.3-7)

Example F.3 If

determine A B. Solution

1 A= 2 1

1 1 0 and B = 2 5

1 1 1 AB = 2 0 2 1 5 (1)(1) + (1)(2) 1 = (2)(1) + (0)(2) = 2 (1)(1) + (5)(2) 9 A matrix A can be multiplied by itself if and only if it is a square matrix. The product A A can be expressed as A2 . If the relevant products are dened, multiplication of matrices is associative, i.e., A(B C) = (A B)C (F.3-8) and distributive, i.e., A(B + C) = A B + A C (B + C)A = B A + C A (F.3-9) (F.3-10)

but, in general, not commutative, i.e., A B 6= B A. For example, if A is of order (m n) and B is of order (n m), then the product A B = C is a matrix of order (m m). On the other hand, the product B A = D is a matrix of order (n n). Even if the matrices A and B are square matrices of the same order, in general, C will be dierent from D. For any unit (or identity) matrix I IA = AI = A F.3.3 Some Properties of Matrices Any row (or column) in a matrix can be modied by multipliying or dividing by a nonzero scalar without aecting the matrix. Any row (or column) can be added or subtracted from another row (or column) without aecting the matrix. Any two rows (or columns) can be interchanged without aecting the matrix. F.4 DETERMINANTS (F.3-11)

For each square matrix A, it is possible to associate a scalar quantity called the determinant of A, |A|. If the matrix A in Eq. (F.1-1) is a square matrix, then the determinant of A is given by a11 a12 a13 ... a1n a21 a22 a23 ... a2n (F.4-1) |A| = ..... ..... ..... ... ..... an1 an2 an3 ... ann 540

If the row and column containing an element aij in a square matrix A are deleted, the determinant of the remaining square array is called the minor of aij and denoted by Mij . The cofactor of aij , denoted by Aij , is then dened by the relation Aij = ( 1)i+j Mij (F.4-2)

Thus, if the sum of the row and column indices of an element is even, the cofactor and the minor of that element are identical; otherwise they dier in sign. The determinant of a square matrix A can be calculated by the following formula: |A| =
n X k=1

aik Aik =

n X k=1

akj Akj

(F.4-3)

where i and j may stand for any row and column, respectively. Therefore, the determinants of (2 2) and (3 3) matrices are a11 a12 (F.4-4) a21 a22 = a11 a22 a12 a21 a11 a12 a13 a21 a22 a23 = a11 a22 a33 + a12 a23 a31 + a13 a21 a32 a31 a32 a33 a11 a23 a32 a12 a21 a33 a13 a22 a31 1 0 1 A = 3 2 1 1 1 0

(F.4-5)

Example F.4 Determine |A| if

Solution Expanding on the rst row, i.e., i = 1, gives 3 2 3 1 2 1 + 1 0 |A| = 1 1 1 1 0 1 0 = 1 + 5 = 4

F.4.1 Some Properties of Determinants If all elements in a row or column a1 b1 a2 b2 0 0 are zero, the determinant is zero, i.e., 0 b1 c1 c1 0 b2 c2 = 0 c2 =0 0 b3 c3 0

(F.4-6)

The value of a determinant is not altered when the rows are changed to columns and the columns to rows, i.e., when the rows and columns are interchanged.

541

 The interchange of any two columns or any two rows of a determinant changes the sign of the determinant. If two columns or two rows of a determinant are identical, the determinant is equal to zero. If each element in any column or row of a determinant is expressed as the sum of two quantities, the determinant can be expressed as the sum of two determinants of the same order, i.e., a1 + d1 b1 c1 a1 b1 c1 d1 b1 c1 a2 + d2 b2 c2 = a2 b2 c2 + d2 b2 c2 (F.4-7) a3 + d3 b3 c3 a3 b3 c3 d3 b3 c3 a1 b1 c1 (a1 + nb1 ) b1 c1 a2 b2 c2 = (a2 + nb2 ) b2 c2 a3 b3 c3 (a3 + nb3 ) b3 c3

Adding the same multiple of each element of one row to the corresponding element of another row does not change the value of the determinant. The same holds true for the columns.

(F.4-8)

If all the elements in any column or row are multiplied by any factor, the determinant is multiplied by that factor, i.e., a1 a1 b1 c1 a2 b2 c2 = a2 a3 a3 b3 c3 (1/)a1 b1 c1 1 a1 (1/)a2 b2 c2 = a2 (1/)a3 b3 c3 a3 b1 c1 b2 c2 b3 c3 b1 c1 b2 c2 b3 c3

(F.4-9)

(F.4-10)

F.5

SPECIAL MATRICES

Transpose of a Matrix The matrix which is obtained from A by interchanging rows and columns is called the transpose of A and denoted by AT . For example, 1 0 1 3 1 T A= 3 2 A = 0 2 1 1 1 A matrix and its transpose are always conformable for multiplication, i.e., A AT = AT A and if A AT = AT A = I then the matrix A is said to be orthogonal. The transpose of the product A B is the product of the transposes in the form (A B)T = BT AT 542 (F.5-3) (F.5-2) (F.5-1)

 Symmetric and Skew-Symmetric Matrices A square matrix A is said to be symmetric if A = AT or aij = aji A square matrix A is said to be skew-symmetric (or antisymmetric ) if A = AT or aij = aji (F.5-5) (F.5-4)

Equation (F.5-5) implies that the diagonal elements of a skew-symmetric matrix are all zero. Singular Matrix A square matrix A for which the determinant |A| of its elements is zero, is termed a singular matrix. If |A| 6= 0, then A is nonsingular. Inverse of a Matrix If the determinant |A| of a square matrix A does not vanish, i.e., nonsingular matrix, it then possesses an inverse (or, reciprocal ) matrix A1 such that A A1 = A1A = I The inverse of a matrix A is dened by A1 = Adj A |A| (F.5-7) (F.5-6)

where Adj A is called the adjoint of A. It is obtained from a square matrix A by replacing each element by its cofactor and then interchanging rows and columns. Example F.5 Find the inverse of the matrix A given in Example F.4. Solution The minor of A is given by 2 1 0 Mij = 1 0 2 The cofactor matrix is 1 0 3 1 3 2 1 0 1 1 1 1 1 1 1 0 = 1 1 1 0 1 1 2 2 1 0 1 1 3 2 3 1

1 0

1 1

5 1 2

The transpose of the cofactor matrix gives the adjoint of A as 1 1 2 Adj A = 1 1 2 5 1 2 543

1 1 5 Aij = 1 1 1 2 2 2

Since |A| = 4, the use of Eq. (F.5-7) gives the inverse of A in the form 0.25 0.25 0.5 Adj A = 0.25 A1 = 0.25 0.5 |A| 1.25 0.25 0.5 Consider the following matrix equation Premultiplication of the both sides of Eq. (F.5-8) by A-1 gives A-1 (A B) = A-1 C (A-1 A)B = A-1 C I B = A-1 C B = A-1 C (F.5-9) AB = C (F.5-8)

This procedure is especially useful in solving systems of linear equations. Example F.6 Solve the following system of algebraic equations x+y+z+w = 7 2x + y 4z + w = 1 3x y + 2z + 2w = 5 2 x 3 y z 3 w = 34 Solution In matrix notation, the given equations are expressed as 7 x 1 1 1 1 2 1 4 1 y = 1 3 1 5 z 2 2 34 w 2 3 1 3 | {z }
A

(1)

Therefore, x = 3, y = 2, z = 1, and w = 7.

where A is the coecient matrix. Premultiplication of the both sides of Eq. (1) by A-1 gives 1 x 1 1 1 1 7 y 2 1 4 1 = 1 z 3 1 2 2 5 w 2 3 1 3 34 3 2 = 1 7

The inverse of the product of two nonsingular square matrices A B is the product of the inverses in the form (F.5-10) (A B)-1 = B-1 A-1 The inverse of a transpose of a matrix is equal to the transpose of its inverse, i.e., (AT )-1 = (A-1 )T 544 (F.5-11)

F.6

LINEAR DEPENDENCE

Consider the x-y coordinate system as shown in Figure F.1.

y
y is independent of x

x is independent of y

Figure F.1 Cartesian coordinate system. The linear combination of x and y is expressed as 1 x + 2 y , where 1 and 2 are nonzero scalars. Let the linear combination of x and y be equal to zero, i.e., 1 x + 2 y = 0 Note that y = 0 on the x-axis, and Eq. (F.6-1) gives 1 x = 0 (F.6-2) (F.6-1)

Since Eq. (F.6-2) must hold for any x, then 1 = 0. On the other hand, x = 0 on the y-axis and Eq. (F.6-1) reduces to (F.6-3) 2 y = 0 Since Eq. (F.6-3) must hold for any y , then 2 = 0. Therefore, when x and y are independent, then the only set of multipliers 1 and 2 which will make 1 x + 2 y = 0 are 1 = 2 = 0. On the other hand, let us consider the case in which y is related to x through the following relationship y = mx (F.6-4) When the linear combination of x and y is equal to zero, Eq. (F.6-1) is still valid. Substitution of Eq. (F.6-4) into Eq. (F.6-1) gives (1 + m 2 ) x = 0 1 + m 2 = 0 1 = m 2 (F.6-5)

Therefore, when x and y are dependent, the equation 1 x + 2 y = 0 is satised when 1 = m 2 . F.6.1 Rank of a Matrix Let A be a matrix of order (m n) in which m is less than n. The determinants formed from the m rows and any m of the n columns are called minors of the matrix A. The rank of a matrix, denoted by rank(A), is equal to the order of the highest order nonvanishing minor. For a square matrix of order (nn), the rst minor will be the determinant of the matrix and of order n. The second minor will be of order (n 1), and so on to the minor of order 1. Example F.7 Determine the rank of the matrix 2 3 1 3 1 3 5 2 4 545

Solution The rst minor is 2 3 1 3 3 3 1 3 1 3 1 3 = 2 + 1 + 3 5 2 5 4 2 4 5 2 4

= 2 (4 + 6) + 3 (12 15) + 1 ( 6 5) = 0

indicating that the rank is not equal to 3. For one of the determinants of order 2, i.e., 1 3 2 4 = 10 6= 0 Therefore, the rank of the given matrix is 2. Comment: Note that the rst minor is zero since the third row is the summation of the rst and second rows. As a result, the rank of a matrix is dened as the number of linearly independent rows (or columns) in the matrix.

Example F.8 Determine the rank of the coecient matrix A in Example F.6. Solution The rst minor is 1 1 1 1 2 1 4 1 = 81 6= 0 3 1 2 2 2 3 1 3

Therefore, the rank of the coecient matrix is 4.

Example F.9 Solve the following system of algebraic equations x+y+z+w = 7 2x + y 4z + w = 1 3x y + 2z + 2w = 5 2 x y + 7 z + 2 w = 13 Solution In matrix notation, the given equations are expressed as x 7 1 1 1 1 2 1 4 1 y = 1 3 1 2 2 z 5 w 13 2 1 7 2 | {z }
A

(1)

546

The solution, however, does not exist because A-1 cannot be calculated. The reason for this is the fact that the determinant of the coecient matrix is zero. Since the fourth equation can be obtained as Fourth eq. = First eq. + Third eq. Second eq. then only three of the given four equations are independent and, the number of unknowns exceeds the number of independent equations.

where A is the coecient matrix. Premultiplication of the both sides of Eq. (1) by A-1 gives 1 7 x 1 1 1 1 y 2 1 4 1 = 1 (2) z 3 1 5 2 2 13 w 2 1 7 2

Comment: Note that the rank of the coecient matrix is three. In other words, the rank of a matrix indicates the number of independent rows.

F.6.2 Reduced Row Echelon Form of a Matrix A matrix is said to be in reduced row echelon form if it satises the following criteria: 1. In each row that does not consist of all zero elements, the rst nonzero element in this row is a 1, called "leading 1". 2. In any two successive rows with nonzero elements, the leading 1 of the lower row occurs farther to the right than the leading 1 of the higher row. 3. All rows consisting entirely of 0 are at the bottom of the matrix. 4. In each column that contains a leading 1 of some row, all other elements of this column are zeros. For example, while the following 1 3 0 0 A= 0 0 0 0 the matrix C matrices A and B are in reduced row echelon form 0 0 5 1 2 0 2 0 1 0 1 B = 0 0 1 0 0 0 1 0 0 0 0 0 1 0 0 0 1 1 3 2 C = 0 1 4 3 1 0 1 2 5

is not in reduced row echelon form since the leading 1 in the second row is not in the left of the leading 1 in the third row. Besides, all the other entries above the leading 1 in the third column are not zero. Every matrix of order (m n) can be transformed to a unique matrix in reduced row echelon form by elementary row operations. Example F.10 Obtain the reduced row exhelon form of the following matrix : 1 1 1 3 7 0 A = 2 3 1 3 2 17 547

Solution 1 1 1 3 2 3 7 0 1 3 2 17 Row 2 = Row 2 2 (Row y Row 3 = Row 3 Row 1 1 1 1 3 0 1 5 6 0 2 3 14 Row 1 = Row 1 Row 2 y Row 3 = Row 3 2 (Row 1 0 4 9 0 1 5 6 0 0 13 26 yRow 3 = Row 3/( 13) 1 0 4 9 0 1 5 6 0 0 1 2 Row 1 = Row 1 + 4 (Row y Row 2 = Row 2 5 (Row 1 0 0 1 0 1 0 4 = rref [A] 0 0 1 2

1)

2)

3) 3)

Comment: The reduced row echelon form of a matrix can be easily obtained by using R MATHCAD .

Consider a system of linear equations given by a11 x1 + a12 x2 + ... + a1n xn = b1 a21 x1 + a22 x2 + ... + a2n xn = b2 . . . am1 x1 + am2 x2 + ... + amn xn = bm In matrix notation, these equations are a11 a12 a21 a22 . . . . . . | expressed as x1 a1n a2n x2 . = . . . . . xn b1 b2 . . .

(F.6-6)

am1 am2 amn {z }

A

bm

548

then, the solutions for the linear system corresponding to [C |d ] is exactly the same as the one corresponding to [A |b ]. In other words, x1 d1 c11 c12 c1n c21 c22 c2n x2 d2 (F.6-9) . = . . . . . . . . . . . . . . cm1 cm2 cmn xn dm Example F.11 Solve the system of algebraic equations given in Example F.6. Solution In matrix notation, the given equations are expressed as 1 1 1 1 x 7 2 1 4 1 y = 1 3 1 2 2 z 5 2 3 1 3 w 34 | {z }
A

Once the augmented matrix [A |b ] can be transformed form [C |d ] by elementary row operations, i.e., c11 c12 c21 c22 n o rref [A |b ] = [C |d ] = . . . . . . cm1 cm2

where A represents the coecient matrix. The augmented matrix is a coecient matrix having an extra column containing the constant terms and this extra column is separated by a vertical line, i.e., a11 a12 a1n b1 a21 a22 a2n b2 (F.6-7) [A |b ] = . . . . . . . . . . . . am1 am2 amn bm c1n c2n . . . d1 d2 . . . dm

to the matrix in reduced row echelon

cmn

(F.6-8)

(1)

The reduced row echelon form (rref) of the augmented matrix, i.e. [C |d ], is given by 1 0 0 0 3 0 1 0 0 2 [C |d ] = 0 0 1 0 1 0 0 0 1 7 549

The augmented matrix, i.e. [A |b ], is given by 1 1 1 1 2 1 4 1 [A |b ] = 3 1 2 2 2 3 1 3

7 1 5 34

(2)

(3)

Since the linear system corresponding to [C |d ] is exactly the same as the one corresponding to [A |b ], then 3 x 1 0 0 0 0 1 0 0 y 2 (4) 0 0 1 0 z = 1 7 w 0 0 0 1 Multiplication yields x = 3 y=2 z=1 w=7

The following two properties related to the reduced row echelon form of a matrix nd widespread application in chemical reaction equilibrium: The rank of a matrix A is equal to the number of nonzero rows in the reduced row echelon form of the matrix A. Example F.12 Determine the rank of the following matrix : 6 2 1 1 0 0 1 2 1 0 0 1 A = 0 0 2 2 0 1 1 1 4 1 2 1 1 Solution The rank of the matrix A is three. On the other, the reduced row echelon form of the matrix A is given by 1 1 1 0 0 2 4 0 1 0 1 1 1 0 rref [A] = 2 0 0 1 0 0 0 0 0 0 0 0 0 0

The number of nonzero rows in the reduced row echelon form is also three.

If multiplication of two matrices is equal to zero, i.e., AB = 0 then rref [A B] = 0 Example F.13 Consider the system of algebraic equations expressed as 4 x1 + x2 + x3 = 0 2 x1 x2 + 3 x3 + x4 = 0 x1 + 2 x2 + x3 3 x4 = 0 550 (F.6-11) (F.6-10)

The reduced row echelon form of the matrix A 1 rref [A] = 0 0 Therefore, Eq. (F.6-11) is written 1 0 0 as 0 0 3 2 1 0 0 1

In matrix notation, the given equations are written as x1 0 4 1 1 0 x 2 0 2 1 3 = 1 x3 0 1 2 1 3 {z } x4 |

A

(1)

is

0 0 3 2 1 0 0 1
7 2 5 2

(2)

or, the given set of equations are expressed as

x1 0 x 7 2 0 = 2 x 3 0 5 x 4 2

(3)

3 x1 x4 = 0 2 x2 + 7 x4 = 0 2 5 x3 + x4 = 0 2

551

Appendix G Constants and Conversion Factors Physical Constants

= 82.05 cm3 . atm/ mol. K = 0.08205 m3 . atm/ kmol. K = 1.987 cal/ mol. K = 8.314 J/ mol. K = 8.314 10 6 MPa. m3 / mol. K = 8.314 10 3 kPa. m3 / mol. K = 8.314 10 5 bar. m3 / mol. K = 8.314 10 2 bar.L/ mol. K = 8.314 10 2 bar. m3 / kmol. K = 83.14 bar. cm3 / mol. K = 9.8067 m/ s2 = 32.1740 ft/ s2

Gas constant (R)

Acceleration of gravity (g ) Avogadros number

6.0221415 1023 entities (atoms or molecules)/ mol

552

Conversion Factors
Density 1 kg/ m3 = 10 3 g/ cm3 = 10 3 kg/L 1 kg/ m3 = 0.06243 lb/ ft3 1 J = 1 W. s = 1 N. m = 10 3 kJ = 105 bar. m3 = 10 bar. cm3 1 cal = 4.184 J 1 kJ = 2.7778 10 4 kW. h = 0.94783 Btu 1 kJ/ kg. K = 0.239 cal/ g. K 1 kJ/ kg. K = 0.239 Btu/ lb.o R 1 N = 1 kg. m/ s2 = 105 g. cm/ s2 (dyne) 1 N = 0.2248 lbf = 7.23275 lb. ft/ s2 (poundals) 1 m = 100 cm = 106 m = 109 nm 1 m = 39.370 in = 3.2808 ft 1 kg = 1000 g 1 kg = 2.2046 lb 1 W = 1 J/ s = 10 3 kW 1 kW = 3412.2 Btu/ h = 1.341 hp 1 Pa = 1 N/ m2 1 kPa = 103 Pa = 10 3 MPa 1 bar = 105 Pa = 100 kPa = 0.98692 atm 1 atm = 1.01325 bar = 101.325 kPa = 760 mmHg 1 atm = 14.696 lbf / in2 1 K = 1.8 o R T ( F) = 1.8 T ( C) + 32 1 m3 = 1000 L 1 m3 = 6.1022 104 in3 = 35.313 ft3 = 264.17 gal

Energy, Heat, Work

Heat capacity Force Length Mass Power

Pressure

Temperature Volume

553

Appendix H Databanks, Simulation Programs, Books, Websites

Finding thermochemical data and selecting proper thermodynamic model are major challenges, among others, in the design of a chemical plant. Some of the commercial and/or free-to-use literature on the subject are provided below. DATABANKS 1. CODATA (The Committee on Data for Science and Technology) http://www.codata.org/resources/databases/key1.html It provides internationally agreed values for the thermodynamic properties of key chemical substances. 2. DETHERM http://i-systems.dechema.de/detherm It provides thermophysical properties of pure substances and mixtures for design and optimization of chemical plants and apparatus. 3. DIPPR (Design Institute for Physical Properties) http://dippr.byu.edu/student.asp Student version of the database provides students to access 100 compounds. 4. Dortmund Data Bank Software Package (DDBSP) http://www.ddbst.de It provides thermodynamic and transport properties of pure components and mixtures for use in process design and development as well as special programs for data correlation, estimation and process synthesis. 5. FactSage http://factsage.com It is an integrated datebase computing system in chemical thermodynamics. 6. Kaye and Laby Online http://www.kayelaby.npl.co.uk It provides tables of physical and chemical constants. 554

7. KDB (Korea Thermophysical Properties Data Bank) http://www.cheric.org/research/kdb It provides information about thermophysical properties and calculation methods for hydrocarbons, light gases, polymers, and electrolyte solutions commonly encountered in chemical engineering practices. 8. NIST (National Institute of Standards and Technology) Chemistry WebBook http://webbook.nist.gov/chemistry It provides chemical and physical property data for various chemical species. 9. NIST/TRC Web Thermo Tables (WTT) http://wtt-pro.nist.gov/cgi-bin/openindex.cgi It provides thermodynamic property data primarily for pure organic compounds. SIMULATION PROGRAMS 1. Aspen HYSYS http://www.aspentech.com/hysys Process simulation of chemical plants and oil reneries. It includes tools for estimation of physical properties and liquid-vapor phase equilibria, heat and material balances, and simulation of many types of chemical engineering equipment. 2. CALPHAD (CALculation of PHAse Diagrams http://www.calphad.org Simulation software for performing thermodynamic and phase diagram calculations. 3. CHEMCAD http://www.chemstations.net Chemical engineering process simulation 4. CompuTherm LLC http://www.computherm.com It provides phase diagram and thermodynamic calculation software tools for industrial, academic, and educational use.

555

5. EQS4WIN (Chemical EQuilibrium Software 4WINdows) http://www.mathtrek.com Calculates equilibrium compositions for reacting systyems. 6. MTDATA http://www.npl.co.uk/advanced-materials/measurement-techniques/modelling/mtdata Software tool for the calculation of phase equilibria and thermodynamic properties. 7. Physical Property Data Service (PPDS) http://www.tuvnel.com/contents/PPDS.aspx It provides key information on more than 15000 chemicals, constant and variable physical properties, thermodynamic model sets, and ash calculations. 8. PRODE http://www.prode.com Solves phase equilibrium separations, prints phase envelopes and phase diagrams, calculates temperature or pressure at dew point, bubble point or specied liquid fraction. 9. ProSim http://www.prosim.net Process simulation and optimization for design and operation of industrial processes. 10. Thermo-Calc http://www.thermocalc.com Simulation software for performing thermodynamic calculations. 11. WinSim http://www.winsim.com Process simulation for chemical and hydrocarbon processes including rening, refrigeration, petrochemical, gas processing, gas treating, pipelines, fuel cells, ammonia, methanol, sulfur and hydrogen facilities. NOTE: It is extremely important to keep in mind that the values obtained from simulation packages do not guarantee correct results. One should understand the thermodynamic assumptions on which the simulation program is based on. For more details on the subject the reader may refer to: Agarwal, R., Y.K. Li, O. Santollani, M.A. Satyro and A. Vieler, 2001, "Uncovering the realities of simulation - Part 1", Chemical Engineering Progress 97 (5), 42-52. Agarwal, R., Y.K. Li, O. Santollani, M.A. Satyro and A. Vieler, 2001, "Uncovering the realities of simulation - Part 2", Chemical Engineering Progress 97 (6), 64-72. 556

BOOKS 1. Assael, M.J., J.P.M. Trusler, T.F. Tsolakis, Thermophysical Properties of Fluids: An Introduction to Their Prediction, Imperial College Press, 1996. 2. Barin, I., Thermophysical Data of Pure Substances, VCH, Weinhem, 1989. 3. DECHEMA - Chemistry Data Series Vol.I Vol. II Vol. III Vol .IV Vol. V Vol. VI Vol. VIII Vol. IX Vol. X Vol. XII Vol. XIV Vol. XV Vapor-Liquid Equilibrium Data Collection Critical Data of Pure Substances Heats of Mixing Data Collection Recommended Data of Selected Compounds and Binary Mixtures Liquid-Liquid Equilibrium Data Collection Vapor-Liquid Equilibria for Mixtures of Low Boiling Substances Solid-Liquid Equilibrium Data Collection Activity Coecients at Innite Dilution Thermal Conductivity and Viscosity Data of Fluid Mixtures Electrolyte Data Collection Polymer Solution Data Collection Solubility and Related Properties of Large Complex Chemicals

4. Millat, J., J.H. Dymond, C.A. Nieto de Castro, Transport Properties of Fluids, Cambridge University Press, 1996. 5. NIST-JANAF Thermochemical Tables, 4th Ed., Chase, M.W. Jr. (Ed.), Springer, 1998. 6. Poling, B.E., J.M. Prausnitz, J.P. OConnell, The Properties of Gases and Liquids, 5th Ed., McGraw-Hill, New York, 2001. 7. TRC Thermodynamic Tables - Hydrocarbons, Ed. Frenkel, M., NIST, Boulder, CO, Standard Reference Data Program, Publication Series NSRDS-NIST-75 (1942-2007), Gaithersburg, MD. 8. TRC Thermodynamic Tables - Non-Hydrocarbons, Ed. Frenkel, M., NIST, Boulder, CO, Standard Reference Data Program, Publication Series NSRDS-NIST-74 (1955-2007), Gaithersburg, MD. 9. Vargaftik, N.B., Y.K. Vinogradov, V.S. Yargin, Handbook of Physical Properties of Liquids and Gases, Third Augmented and Revised Ed., Begell House, New York, 1996. 10. Yaws, C.L., Thermodynamic and Physical Property Data, Gulf Pub. Company, Houston, Texas, 1992.

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WEBSITES 1. Chemical Reaction Stoichiometry (CRS) hhtp://www.chemical-stoichiometry.net 2. Gibbs Models http://www.iastate.edu/~jolls 3. Macatea Productions - Thermo Workshop http://www.macatea.com/wshop 4. Nano, Quantum & Statistical Mechanics & Thermodynamics Educational Sites http://tigger.uic.edu/~mansoori/Thermodynamics.Educational.Sites_html 5. Thermographics http://www.owlnet.rice.edu/~wgchap/Phase/v3dcmnt.htm

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